Polyester-ether resin blends

ABSTRACT

The present application relates to novel polyester-ether compositions and their use as oxygen scavenging materials in polyester resins.

FIELD OF THE INVENTION

The present application relates to novel polyester-ether compositionsand their use in polyester resins.

BACKGROUND

Polyesters have been replacing glass and metal packaging materials dueto their lighter weight, decreased breakage compared to glass, andpotentially lower cost. One major deficiency with standard polyesters,however, is its relatively high gas permeability. This curtails theshelf life of carbonated soft drinks and oxygen sensitive beverages orfoodstuff such as beer, wine, tea, fruit juice, ketchup, cheese and thelike. Organic oxygen scavenging materials have been developed partly inresponse to the food industry's goal of having longer shelf-life forpackaged food. These oxygen scavenging materials are incorporated intoat least a portion of the package and remove oxygen from the enclosedpackage volume which surrounds the product or which may leak into thepackage, thereby inhibiting spoilage and prolonging freshness.

Suitable oxygen scavenging materials include oxidizable organic polymerswhich may react with ingressing oxygen. One example of an oxidizableorganic polymer is a polyether. The polyether is typically used as apolyester-ether copolymer and in low amounts of less than 10 weightpercent of the packaging material. The polyester-ether is dispersed inthe matrix polyester phase and interacts with a suitable oxygenscavenging catalyst that catalyzes the reaction of the ingressing oxygenwith the polyether. Oxygen scavenging catalysts are typically transitionmetal compounds, for example an organic or inorganic salt of cobalt.Other examples include manganese, copper, chromium, zinc, iron andnickel.

Polyester containers comprising polyester-ethers and an oxygenscavenging catalyst show excellent oxygen barrier properties. However,polyethers are also lacking in stability. During preparation andprocessing the polyether-containing material into articles andcontainers, undesirable degradation products such as acetaldehyde,tetrahydrofuran, and other C₂- to C₄-molecules may be produced invarious amounts. These side products can inter alia cause undesirableoff-tastes in the product. The problem is aggravated by the presence ofthe transition metal oxygen scavenging catalyst. The oxygen scavengingcatalyst may also catalyze polyether degradation reactions. However, thetransition metal based oxygen scavenging catalyst may impart color tothe resin and may catalyze unwanted degradation processes in the resin.Therefore, it is often desirable to minimize the amount of metal basedoxygen scavenging catalysts.

The amount of degradation products may in turn be reduced by addingstabilizers to the resin blend. It is commonly believed that thesestabilizers reduce the amount of degradation products by scavengingradicals generated during production of the resins and their processingto the final articles. However, the use of such stabilizers isconsidered to be problematic in its own way: Stabilizers are consideredto attenuate all radical reactions. Since the oxygen scavenging reactionalso involves a transition metal-catalyzed radical mechanism, thepresence of such stabilizers is considered to also negatively affect theoxygen barrier properties. In other words, the use of stabilizersreduces side-products in the packaging material but also deterioratesthe oxygen barrier properties. Therefore, the use of stabilizers islimited in practical application.

There is a need in the art to provide polyether-containing resins whichhave reduced amounts of degradation products such as acetaldehyde,tetrahydrofuran, and other C₂- to C₄-molecules but still providedexcellent oxygen-scavenging properties.

For some applications, for example juice applications, it isadvantageous that the induction time, i.e. the time lapsed until thebarrier material effectively scavanges ingressing oxygen, is as short aspossible. Many polyester-ether containing polyester resins provideoverall excellent barrier properties but have rather long inductiontimes. Thus, there is a need for barrier materials that have shorterinduction times.

One method of addressing gas permeability involves incorporating anoxygen scavenger into the package structure itself. In such anarrangement, oxygen scavenging materials constitute at least a portionof the package, and these materials remove oxygen from the enclosedpackage volume which surrounds the product or which may leak into thepackage, thereby inhibiting spoilage and prolonging freshness in thecase of food products.

Suitable oxygen scavenging materials include oxidizable organic polymersin which either the backbone or the side-chains of the polymer reactwith oxygen. Such oxygen scavenging materials are typically employedwith a suitable catalyst, for example, an organic or inorganic salt of atransition metal such as cobalt.

One example of an oxidizable organic polymer is a polyether. Thepolyether is typically used as polyester-ether copolymer and in lowamounts of less than 10 weight percent of the packaging material.Typically, the polyester-ether is dispersed in the polyester phase andforms discrete domains within this phase.

Polyester containers comprising polyester-ethers and an oxidationcatalyst show excellent oxygen barrier properties, but suffer from adelamination phenomenon: When such containers are subjected to shock,e.g. by dropping the container from greater heights, the container maydelaminate. This is a surprising type of material failure since thecontainer is a monolayer bottle made from a homogeneous blend ofpolyester and polyester-ether. Nevertheless, the bottle delaminates asif it is made of a multilayer material. Delamination is a major concernfor the packaging industry since delaminated containers may leak andsince customers may not be willing to accept defects in appearancecaused by delamination. In addition, delamination may have a negativeimpact on barrier properties. Also in film applications delamination maybe undesirable.

There is a need in the art to provide oxygen-scavenging materials havinga reduced delamination behavior.

SUMMARY OF THE INVENTION First Aspect

It was now surprisingly found that certain hindered amine lightstabilizers (HALS) are, on the one hand, particularly efficient inreducing the above-mentioned degradation products inpolyester-ether-compositions and, on the other hand, do not excessivelyreduce oxygen barrier properties.

Accordingly, in one aspect, there is provided a composition forpreparing an article, preform or container comprising:

-   -   a) 80-98.5 parts by weight of a base polyester;    -   b) 0.5-20 parts by weight of a copolyester-ether,        -   b1) wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments,        -   b2) wherein the one or more polyether segments are present            in an amount of about 5 to about 95 wt.-% of the            copolyester-ether,        -   b3) wherein the weight ratio of the one or more polyether            segments to the total amount of base polyester and polyester            segments in the composition is 0.2-10 wt.-%;    -   c) a transition metal-based oxidation catalyst; and    -   d) a monomeric, oligomeric or polymeric hindered amine light        stabilizer (HALS) in an amount of 15-10,000 ppm, on basis of the        weight of the stabilizer in the total composition, wherein the        HALS is represented by the formula (I) or a mixture of compounds        of formula (I),

wherein each R₁ independently represents C₁-C₄ alkyl, R₂ represents H,C₁-C₄ alkyl, OH, O—C₁-C₄ alkyl, or a further part of an oligomeric orpolymeric HALS, and R₃ represents a further part of a monomeric,oligomeric or polymeric HALS.

There are also provided articles, preforms and containers comprising orprepared from such a composition.

In another aspect, there is provided a masterbatch for use in preparingan article, preform or container comprising:

-   -   a) copolyester-ether, wherein the copolyester-ether comprises        one or more polyester segments and one or more polyether        segments, wherein the one or more polyether segments are present        in an amount of about 5 to about 95 wt.-% of the        copolyester-ether; and    -   b) a monomeric, oligomeric or polymeric hindered amine light        stabilizer (HALS) in an amount of 100-30,000 ppm, on basis of        the weight of the stabilizer in the total composition, wherein        the HALS is represented by the formula (I) or a mixture of        compounds of formula (I),

wherein each R₁ independently from each represents C₁-C₄ alkyl, R₂represents H, C₁-C₄ alkyl, OH, O—C₁-C₄ alkyl, or a further part of anoligomeric or polymeric HALS, and R₃ represents a further part of amonomeric, oligomeric or polymeric HALS. The masterbatch preferably doesnot contain inorganic (tinting) pigments in an amount of above 0.6 wt.-%of the total masterbatch and carbon black in an amount of above 1.2wt.-% of the total masterbatch. The masterbatch is preferably not aslush molded elastomeric composition, layer or article.

In another aspect, there is provided a method of preparing a masterbatchfor use in preparing an article, preform or container comprising mixinga copolyester-ether, wherein the copolyester-ether comprises one or morepolyester segments and one or more polyether segments, wherein the oneor more polyether segments are present in an amount of about 5 to about95 wt.-% of the copolyester-ether; with a monomeric, oligomeric orpolymeric hindered amine light stabilizer (HALS) in an amount of100-30,000 ppm, on basis of the weight of the stabilizer in the totalcomposition, wherein the HALS is represented by the formula (I) or amixture of compounds of formula (I),

wherein each R₁ independently represents C₁-C₄ alkyl, R₂ represents H,C₁-C₄ alkyl, OH, O—C₁-C₄ alkyl, or a further part of an oligomeric orpolymeric HALS, and R₃ represents a further part of a monomeric,oligomeric or polymeric HALS.

In another aspect, there is provided a method of preparing a compositionfor use in preparing an article, preform or container comprising mixing80-98.5 parts by weight of a base polyester with:

-   -   a) 0.5-20 parts by weight of a copolyester-ether, wherein the        copolyester-ether comprises one or more polyester segments and        one or more polyether segments, wherein the one or more        polyether segments are present in an amount of about 5 to about        95 wt.-% of a copolyester-ether,    -   b) a transition metal-based oxidation catalyst; and    -   c) a monomeric, oligomeric or polymeric hindered amine light        stabilizer (HALS) in an amount of 15-10,000 ppm, on basis of the        weight of the stabilizer in the total composition, wherein the        HALS is represented by the formula (I) or a mixture of compounds        of formula (I),

wherein each R₁ independently represents C₁-C₄ alkyl, R₂ represents H,C₁-C₄ alkyl, OH, O—C₁-C₄ alkyl, or a further part of an oligomeric orpolymeric HALS, and R₃ represents a further part of a monomeric,oligomeric or polymeric HALS.

In another aspect, there is provided the use of a monomeric, oligomericor polymeric hindered amine light stabilizer (HALS), wherein the HALS isrepresented by the formula (I) or a mixture of compounds of formula (I),

wherein each R₁ independently represents C₁-C₄ alkyl, R₂ represents H,C₁-C₄ alkyl, OH, O—C₁-C₄ alkyl, or a further part of an oligomeric orpolymeric HALS, and R₃ represents a further part of a monomeric,oligomeric or polymeric HALS; for reducing the amount of decompositionproducts in an article, preform or container comprising: 80-98.5 partsby weight of a base polyester; 0.5-20 parts by weight of acopolyester-ether, wherein the copolyester-ether comprises one or morepolyester segments and one or more polyether segments, and wherein theone or more polyether segments are present in an amount of about 5 toabout 95 wt.-% of the copolyester-ether, and a transition metal-basedoxidation catalyst.

Second Aspect

It was now found that the introduction of a titanium compound into thepolymer resin improves oxygen barrier properties if the resin furthercomprises a traditional transition metal-based oxidation catalyst suchas a cobalt compound. This is highly surprising since the very sametitanium compound provides only poor oxygen barrier properties on itsown. Without wishing to be limited by theory, it appears that thetitanium compound acts as a co-catalyst in combination with thetransition metal-based oxidation catalyst and that both compounds worktogether in a complementary manner to surprisingly improve oxygenbarrier properties of the resin. Furthermore, already a very smallamount of the titanium compound provides a very substantial increase inoxygen barrier properties. Thus, the overall amount of transition metalsin the resin can be reduced. Most advantageously, it is possible to usethe titanium compound as transesterfication or polycondensationcatalyst. If the titanium compound has such a dual purpose, the overallamount of transition metals in the resin can even be further reduced.

Accordingly, in one aspect, there is provided a composition forpreparing articles, preforms or containers comprising:

-   -   a) 80-99.5 parts by weight of a base polyester;    -   b) 0.5-20 parts by weight of a copolyester-ether, wherein the        copolyester-ether comprises one or more polyester segments and        one or more polyether segments; and    -   c) a transition metal-based oxidation catalyst,        -   c1) wherein the transition metal is selected from cobalt,            manganese, copper, chromium, zinc, iron, and nickel, and        -   c2) wherein the transition metal based oxidation catalyst is            present in an amount of 10-500 ppm, on basis of the weight            of the transition metal in the total composition; and;    -   d) a titanium compound,

wherein the weight ratio of the transition metal-based oxidationcatalyst to the titanium compound, on basis of the weight of thetransition metal and the titanium, is from 50:1 to 1:1.

In another aspect, there is provided a “salt-and-pepper” mixture ofmasterbatches, more specifically a kit-of-parts for use in preparingarticles, preforms or containers comprising two masterbatches which mayoptionally be in admixture:

a first masterbatch comprising:

-   -   a) a base polyester,    -   b) a transition metal-based oxidation catalyst, wherein the        transition metal is selected from cobalt, manganese, copper,        chromium, zinc, iron, and nickel, and    -   c) a titanium compound, wherein the titanium compound is present        in an amount of about 5 to about 500 ppm, on basis of the weight        of the titanium in the first masterbatch; and a second        masterbatch comprising:    -   d) a copolyester-ether; and optionally    -   e) one or more antioxidants.

In another aspect, there are provided an article, preform or containerprepared from a composition or kit-of-parts of the above aspects.

In another aspect, there is provided a method of preparing a compositionfor use in preparing articles, preforms or containers comprising mixing:

-   -   a) 80-99.5 parts by weight of a base polyester;    -   b) 0.5-20 parts by weight of a copolyester-ether, wherein the        copolyester-ether comprises one or more polyester segments and        polyether segments; and    -   c) a transition metal-based oxidation catalyst,        -   c1) wherein the transition metal is selected from cobalt,            manganese, copper, chromium, zinc, iron, and nickel, and        -   c2) wherein the transition metal based oxidation catalyst is            present in an amount of 10-500 ppm, on basis of the weight            of the transition metal in the total composition; and    -   d) a titanium compound;

wherein the weight ratio of the transition metal-based oxidationcatalyst to the titanium compound, on basis of the weight of thetransition metal and the titanium, is from 50:1 to 1:1.

In still another aspect, there is provided a method of preparing akit-of-parts for use in preparing articles, preforms or containerscomprising combining two masterbatches, the first masterbatchcomprising:

-   -   a) a base polyester,    -   b) a transition metal-based oxidation catalyst, wherein the        transition metal is selected from cobalt, manganese, copper,        chromium, zinc, iron, and nickel, and    -   c) a titanium compound, wherein the titanium compound is present        in an amount of about 5 to about 500 ppm, on basis of the weight        of the titanium in the first masterbatch; and the second        masterbatch comprising:    -   d) a copolyester-ether; and optionally    -   e) one or more antioxidants.

Third Aspect

Accordingly, in one aspect, there is provided a composition forpreparing articles, preforms or containers comprising:

-   -   a) 80-99.5 parts by weight of a base polyester;    -   b) 0.5-20 parts by weight of a copolyester-ether,        -   b1) wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments, and        -   b2) wherein the one or more polyether segments are present            in an amount of 5 to 45 wt.-% of the copolyester-ether;    -   c) a transition metal-based oxidation catalyst,        -   c1) wherein the transition metal is selected from cobalt,            manganese, copper, chromium, zinc, iron, and nickel, and        -   c2) wherein the transition metal based oxidation catalyst is            present in an amount of 10-500 ppm, on basis of the weight            of the transition metal in the total composition; and    -   d) a titanium compound.

In one aspect of the invention, there is provided a kit-of-parts for usein preparing articles, preforms or containers comprising twomasterbatches which may optionally be in admixture:

the first masterbatch comprising:

-   -   a) a base polyester,    -   b) a transition metal-based oxidation catalyst, wherein the        transition metal is selected from cobalt, manganese, copper,        chromium, zinc, iron, and nickel, and wherein the transition        metal based oxidation catalyst is present in an amount of        500-15000 ppm, on basis of the weight of the transition metal in        first masterbatch,    -   c) a titanium compound; and        the second masterbatch comprising:    -   d) a copolyester-ether,        -   d1) wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments, and        -   d2) wherein the one or more polyether segments are present            in an amount of 5 and 45 wt.-% in the copolyester-ether; and            optionally    -   e) one or more antioxidants.

In one aspect of the invention, there are provided an article, preformor container prepared from a composition or a kit-of-parts of the aboveaspects.

In still another aspect, there is provided a method of preparing acomposition for use in preparing articles, preforms or containerscomprising mixing:

-   -   a) 80-99.5 parts by weight of a base polyester;    -   b) 0.5-20 parts by weight of a copolyester-ether,        -   b1) wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments, and        -   b2) wherein the one or more polyether segments are present            in an amount of 5 to 45 wt.-% of the copolyester-ether;    -   c) a transition metal-based oxidation catalyst,        -   c1) wherein the transition metal is selected from cobalt,            manganese, copper, chromium, zinc, iron, and nickel, and        -   c2) wherein the transition metal based oxidation catalyst is            present in an amount of 10-500 ppm, on basis of the weight            of the transition metal in the total composition; and    -   d) a titanium compound.

In another aspect, there is provided a method of preparing akit-of-parts for use in preparing articles, preforms or containerscomprising combining two masterbatches

the first masterbatch comprising:

-   -   a) a base polyester,    -   b) a transition metal-based oxidation catalyst, wherein the        transition metal is selected from cobalt, manganese, copper,        chromium, zinc, iron, and nickel, and wherein the transition        metal based oxidation catalyst is present in an amount of        500-15000 ppm, on basis of the weight of the transition metal in        first masterbatch,    -   c) a titanium compound; and        the second masterbatch comprising:    -   d) a copolyester-ether,        -   d1) wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments, and        -   d2) wherein the one or more polyether segments are present            in an amount of 5 and 45 wt.-% in the copolyester-ether; and            optionally    -   e) one or more antioxidants.

Fourth Aspect

It was surprisingly found that polyester articles comprising thepolyester-ethers of the present invention show reduced delamination. Itwas further found that delamination is reduced if the melting point ofthese copolyester-ethers is matched to be in the region of the meltingpoint of the polyester used as base resin to prepare the container.Since polyesters used for container applications typically have meltingpoints of about 240-250° C., this means that those copolyester-ethers ofthe present invention having melting points between about 225° C. and250° C. are particularly suitable for reducing delamination incontainers.

Without wishing to be bound by theory, it is believed that the reasonfor the observed reduced delamination is that localized stress inducedby e.g. dropping the container is more readily relaxed in the containerwall if the copolyester-ether domains are formed from thecopolyester-ethers of the present invention. This is supported by thefinding that the reduced delamination behavior correlates with themelting point of the copolyester-ethers of the present invention. Againwithout wishing to be bound by theory, it appears that viscousdissipation of fracture energy is favored by matching the melting pointsof the polyester base resin and the copolyester-ether of the presentinvention.

Accordingly, in one aspect, there is provided a composition forpreparing an article, preform or container comprising:

-   -   a) 80-99.5 parts by weight of a base polyester;    -   b) 0.5-20 parts by weight of a copolyester-ether, wherein the        copolyester-ether comprises one or more polyester segments and        one or more polyether segments, wherein the one or more        polyether segments are present in an amount of about 5 to about        45 wt.-% of the copolyester-ether; and    -   c) a transition metal-based oxidation catalyst;        wherein the melting point difference, determined according to        ASTM D 3418-97, between the base polyester and the        copolyester-ether is less than 15° C.

There are also provided an article or preform comprising or preparedfrom such a composition as well as a container comprising or preparedfrom such a composition or preform.

In another aspect, there is provided a masterbatch for use in preparingan article, preform or container comprising, preferably consisting of:

-   -   a) a copolyester-ether,        -   a1) wherein the copolyester-ether comprises one or more            polyethylene terephthalate (co)polymer segments and one or            more linear or branched poly (C₂-C₆-alkylene glycol)            segments,        -   a2) wherein the one or more polyether segments are present            in an amount of from about 5 to about 45 wt.-% in the            copolyester-ether, and        -   a3) wherein the melting point, determined according to ASTM            D 3418-97, of the copolyester-ether is from 225° C. to 250°            C.; and    -   b) from 20 to 5000 ppm, on basis of the weight of the one or        more linear or branched poly (C₂-C₆-alkylene glycol) segments,        of one or more antioxidants selected from group consisting of        hindered phenols, benzophenones, sulfur-based antioxidants,        phosphites and hindered amine light stabilizers.

The masterbatch may optionally comprise, preferably consist of, one ormore of a polyester or a copolyester, a transition metal-based oxidationcatalyst, an ionic compatibilizer and one or more additives selectedfrom the group consisting of dyes, pigments, fillers, branching agents,reheat agents, anti-blocking agents, anti-static agents, biocides,blowing agents, coupling agents, flame retardants, heat stabilizers,impact modifiers, crystallization aids, lubricants, plasticizers,processing aids, buffers, and slip agents.

In another aspect, there is provided a copolyester-ether comprising oneor more polyethylene terephthalate (co)polymer segments and one orpoly(butylene glycol) or poly(propylene glycol) segments, wherein theone or more poly(butylene glycol) or poly(propylene glycol) segments arepresent in an amount of from about 20 to about 35 wt.-% in thecopolyester-ether, and having a melting point, determined according toASTM D 3418-97, of from 225° C. to 250° C.

In another aspect, there is provided a method of preparing an article,preform or container, wherein 80-99.5 parts by weight of a basepolyester are blended with:

a) 0.5-20 parts by weight of a copolyester-ether, wherein thecopolyester-ether comprises one or more polyester segments and one ormore polyether segments, wherein the one or more polyether segments arepresent in an amount of about 5 to about 45 wt.-% of thecopolyester-ether; andb) a transition metal-based oxidation catalyst; wherein the meltingpoint difference, determined according to ASTM D 3418-97, between thepolyester and the copolyester-ether is less than 15° C.

In another aspect, there is provided the use of a copolyester-ether forpreparing an article, preform or container; wherein thecopolyester-ether comprises one or more polyester segments and one ormore polyether segments, and wherein the one or more polyether segmentsare present in the copolyester-ether in an amount of from about 5 toabout 45 wt.-%, and wherein the melting point of the copolyester-ether,determined according to ASTM D 3418-97, is from 225° C. to 250° C.

There is also provided the use of such a copolyester-ether for preparinga kit-of-parts comprising said copolyester-ether and physical orelectronic instructions or advises to use said copolyester-ether forpreparing a preform or container.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a line graph depicting oxygen ingress in titanium containingblends of samples 5, 6 and 7.

DETAILED DESCRIPTION

The following detailed description of components is applicable to all ofthe above-mentioned aspects of the present invention. In addition,individual elements of the detailed description are intended to befreely combinable with the above various aspects of the invention.

Generally, polyesters suitable for the present invention can be preparedby one of two processes, namely: (1) the ester process and (2) the acidprocess. The ester process is where a dicarboxylic ester (such asdimethyl terephthalate) is reacted with ethylene glycol or other diol inan ester interchange reaction. Catalysts for use in the esterinterchange reaction are well known and may be selected from manganese,zinc, cobalt, titanium, calcium, magnesium or lithium compounds. Becausethe reaction is reversible, it is generally necessary to remove thealcohol (e.g. methanol when dimethyl terephthalate is employed) tocompletely convert the raw materials into monomers. The catalyticactivity of the interchange reaction catalyst may optionally besequestered by introducing a phosphorus compound, for examplepolyphosphoric acid, at the end of the ester interchange reaction. Thenthe monomer undergoes polycondensation. The catalyst employed in thisreaction is typically an antimony, germanium, aluminum, zinc, tin ortitanium compound, or a mixture of these. In some embodiments, it may beadvantageous to use a titanium compound. In the second method for makingpolyester, an acid (such as terephthalic acid) is reacted with a diol(such as ethylene glycol) by a direct esterification reaction producingmonomer and water. This reaction is also reversible like the esterprocess and thus to drive the reaction to completion one must remove thewater. The direct esterification step does not require a catalyst. Themonomer then undergoes polycondensation to form polyester just as in theester process, and the catalyst and conditions employed are generallythe same as those for the ester process. In summary, in the esterprocess there are two steps, namely: (1) an ester interchange, and (2)polycondensation. In the acid process there are also two steps, namely:(1) direct esterification, and (2) polycondensation.

Suitable polyesters can be aromatic or aliphatic polyesters, and arepreferably selected from aromatic polyesters. An aromatic polyester ispreferably derived from one or more diol(s) and one or more aromaticdicarboxylic acid(s). The aromatic dicarboxylic acid includes, forexample, terephthalic acid, isophthalic acid, 1,4-, 2,5-, 2,6- or2,7-naphthalenedicarboxylic acid and 4,4′-diphenyldicarboxylic acid (andof these terephthalic acid is preferred). The diol is preferablyselected from aliphatic and cycloaliphatic diol(s), including, forexample, ethylene glycol, 1,4-butanediol, 1,4-cyclohexane dimethanol,and 1,6-hexanediol (and of these, aliphatic diols, and preferablyethylene glycol, is preferred). Preferred polyesters are polyethyleneterephthalate (PET) and polyethylene-2,6-naphthalene dicarboxylate (alsoreferred to herein as polyethylene-2,6-naphthalate), and particularlypreferred is PET.

Examples of suitable polyesters include those produced from the reactionof a diacid or diester component comprising at least 65 mol.-% aromaticdiacid (preferably terephthalic acid) or the C₁-C₄ dialkyl ester of thearomatic acid (preferably C₁-C₄ dialkylterephthalate), for example atleast 70 mol.-% or at least 75 mol.-% or at least 95 mol.-%, with a diolcomponent comprising at least 65 mol.-% diol (preferably ethyleneglycol), for example at least 70 mol. % or at least 75 mol-% or at least95 mol.-%. Exemplary polyesters include those wherein the diacidcomponent is terephthalic acid and the diol component is ethyleneglycol, thereby forming polyethylene terephthalate (PET). The molepercent for all the diacid components totals 100 mol.-%, and the molepercentage for all the diol components totals 100 mol.-%.

The polyester may be modified by one or more diol components other thanethylene glycol. In this case, the polyester is a copolyester. Suitablediol components of the described polyester may be selected from1,4-cyclohexane-dimethanol, 1,2-propanediol, 1,4-butanediol,2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol (2MPDO)1,6-hexanediol, 1,2-cyclo-hexanediol, 1,4-cyclohexanediol,1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and diolscontaining one or more oxygen atoms in the chain, e.g., diethyleneglycol, triethylene glycol, dipropylene glycol, tripropylene glycol ormixtures of these, and the like. In general, these diols contain 2 to18, preferably 2 to 8 carbon atoms. Cycloaliphatic diols can be employedin their cis- or trans-configuration or as mixture of both forms.Suitable modifying diol components can be 1,4-cyclohexanedimethanol ordiethylene glycol, or a mixture of these.

The polyester may be modified by one or more acid components other thanterephthalic acid. In this case, the polyester is a copolyester.Suitable acid components (aliphatic, alicyclic, or aromatic dicarboxylicacids) of the linear polyester may be selected, for example, fromisophthalic acid, 1,4-cyclohexanedicarboxylic acid,1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipicacid, sebacic acid, 1,12-dodecanedioic acid,2,6-naphthalene-dicarboxylic acid, bibenzoic acid, or mixtures of theseand the like. In the polymer preparation, it is possible to use afunctional acid derivative of the above acid components. Typicalfunctional acid derivatives include the dimethyl, diethyl, or dipropylester of the dicarboxylic acid or its anhydride.

As used herein, the term “base polyester” refers to a polyestercomponent which is the predominant component of the total composition,i.e. used in excess of 50 wt.-% of the total composition, in particularin excess of 80 wt.-%, more specifically in excess of 90 wt.-%.

Advantageously, the polyester is a copolyester of ethylene glycol with acombination of terephthalic acid and isophthalic acid and/or5-sulfoisophthalic acid. Generally, the isophthalic acid can be presentfrom about 0.05 mol.-% to about 10 mol.-% and the 5-sulfoisophthalicacid from can be present from about 0.1 mol.-% to about 3 mol.-% of thecopolymer.

Advantageously, the polyester is selected from polyethyleneterephthalate, polyethylene naphthalate, polyethylene isophthalate,copolymers of polyethylene terephthalate, copolymers of polyethylenenaphthalate, copolymers of polyethylene isophthalate, or mixturesthereof; for example the polyester can be a copolymer of polyethyleneterephthalate, such as poly(ethylene terephthalate-co-ethyleneisophthalate) or poly(ethylene terephthalate-co-ethylene5-sulfoisophthalate).

First Aspect

The composition for preparing an article, preform or container comprises80-98.5 parts by weight of a base polyester, including 85-98.5, 90-98.5,or 95-98.5 parts by weight of the base polyester. Preferably, thecomposition comprises 90-98.5 parts by weight of the base polyester.

Copolyester-ethers suitable for the present invention comprise one ormore polyester segments and one or more polyether segments having anumber-average molecular weight of from about 200 to about 5000 g/mol.Advantageously, the copolyester-ether has a number-average molecularweight of from about 600 to about 2500 g/mol, more specifically about800 to about 1800 g/mol or about 1000 to about 1600 g/mol. TheCopolyester-ethers are present in the composition in an amount from0.5-20 parts by weight, including 0.5-15 parts by weight, 0.5-10 partsby weight, and 0.5-5 parts by weight. Preferably, the compositioncomprises 0.5-10 parts by weight of the copolyester-ethers.

The one or more polyether segments may advantageously be present in anamount of about 5 to about 60 wt.-% of the copolyester-ether.Advantageously, the polyether segments are present in an amount of about10 to about 45 wt.-%, more specifically about 20 to about 40 wt.-%, orin particular about 25 to about 35 wt.-% or about 25 to about 30 wt.-%,in all cases based on the copolyester-ether.

Generally, copolyester-ethers suitable for the present inventioncomprise one or more polyether segments in amounts so that the weightratio of the one or more polyether segments to the total amount of basepolyester and polyester segments in the composition is about 0.2 toabout 15 wt.-%, more specifically about 0.5 to about 10 wt.-%, or inparticular about 0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-%,or about 1 to about 2.5 wt.-%. Advantageously, the polyether segment isa poly (C₂-C₆-alkylene glycol) segment. The C₂-C₆-alkylene glycol may bea linear or branched aliphatic C₂-C₆-moiety. Specific examples of suchcopolyester-ethers include poly(ethylene glycol), linear or branchedpoly(propylene glycol), linear or branched poly(butylene glycol), linearor branched poly(pentylene glycol), linear or branched poly(hexyleneglycol) as well as mixed poly (C₂-C₆-alkylene glycols) obtained from twoor more of the glycolic monomers used in preparing the before-mentionedexamples. Advantageously, the polyether segment is a linear or branchedpoly(propylene glycol) or a linear or branched poly(butylene glycol).

The copolyester-ethers suitable for the present invention also compriseone or more polyester segments. The type of polyester in these segmentsis not particularly limited and can be any of the above-referencedpolyesters. Advantageously, the copolyester-ether comprises apolyethylene terephthalate (co)polymer segment. Advantageously, thecopolyester-ether comprises a polyethylene terephthalate (co)polymersegment and a linear or branched poly(butylene glycol) segment.

The composition for preparing an article, preform or container comprises0.5-20 parts by weight of a copolyester-ether, including 0.5-15, 0.5-10,and 0.5-5 parts by weight of the copolyester-ether. Preferably, thecomposition comprises 0.5-10 parts by weight of the copolyester-ether.

Methods of preparing polyethers and copolyester-ethers are well known inthe art. For example, the copolyester-ether can be produced by esterinterchange with the dialkyl ester of a dicarboxylic acid. In the esterinterchange process dialkyl esters of dicarboxylic acids undergotransesterification with one or more glycols in the presence of acatalyst such as zinc acetate as described in WO 2010/096459 A2,incorporated herein by reference. A suitable amount of elemental zinc inthe copolyester-ether can be about 35 to about 100 ppm, for exampleabout 40 to about 80 ppm, by weight of the copolyester-ether. Thepoly(alkylene oxide) glycols replace part of these glycols in thesetransesterification processes. The poly(alkylene oxide) glycols can beadded with the starting raw materials or added aftertransesterification. In either case, the monomer and oligomer mixturecan be produced continuously in a series of one or more reactorsoperating at elevated temperature and pressures at one atmosphere orlesser. Alternatively, the monomer and oligomer mixture can be producedin one or more batch reactors. Suitable conditions for these reactionsare temperatures of from about 180° C. to 250° C. and pressures of fromabout 1 bar to 4 bar.

Next, the mixture of copolyester-ether monomer and oligomers undergoesmelt-phase polycondensation to produce a polymer. The polymer isproduced in a series of one or more reactors operating at elevatedtemperatures. To facilitate removal of excess glycols, water, and otherreaction products, the polycondensation reactors are run under a vacuum.Catalysts for the polycondensation reaction include compounds ofantimony, germanium, tin, titanium and/or aluminum. In some embodiments,it may be advantageous to use a titanium compound. A suitable amount ofelemental Ti can be about 5 to about 60 ppm, for example about 10 toabout 35 ppm. Reaction conditions for polycondensation can include (i) atemperature less than about 290° C., or about 10° C. higher than themelting point of the copolyester-ether; and (ii) a pressure of less thanabout 0.01 bar, decreasing as polymerization proceeds. Thiscopolyester-ether can be produced continuously in a series of one ormore reactors operating at elevated temperature and pressures less thanone atmosphere. Alternatively this copolyester-ether can be produced inone or more batch reactors. The intrinsic viscosity after melt phasepolymerization can be in the range of about 0.5 dl/g to about 1.5 dl/g.Antioxidants and other additives can be added before and/or duringpolymerization to control the degradation of the polyester-ethersegments. Alternatively, the copolyester-ethers can be produced byreactive extrusion of the polyether with the polyester. In theabove-described methods of preparing the copolyester-ethers, it mayhappen that the polyether does not fully react with the polyester but ispartly present as an intimate blend of the polyester and polyether.Therefore, throughout the specification and embodiments, the referenceto a copolyester-ether comprising one or more polyester segments and oneor more polyether segments is to be understood as referring to therespective copolyester-ethers, blends of respective polyesters andpolyethers, and mixtures comprising both the respectivecopolyester-ethers and blends of the respective polyesters andpolyethers.

The copolyester-ether is preferably used in amounts of about 0.5 toabout 20 wt.-% in relation to the final composition. Advantageously, theamount of the copolyester-ether is selected within the range of about0.5 to about 10 wt.-%, in relation to the final container, preform andarticle composition, so that the amount of polyether segments to thetotal amount of base polyester and polyester segments in the compositionis about 0.2 to about 10 wt.-%, more specifically about 0.5 to about 10wt.-%, or in particular about 0.7 to about 5 wt.-%, or about 0.5 toabout 1.5 wt.-% or about 1 to about 2.5 wt.-%.

Advantageously, the copolyester-ether contains one or more polyethersegments in an amount of about 5 to about 45 wt.-%, in particular about15 to about 45 wt.-%, more specifically about 20 to about 40 wt.-%, andalso in particular about 15 to about 35 wt.-%, more specifically about20 to about 30 wt.-%, and that the amount of the copolyester-ether isselected so that the amount of polyether segments to the total amount ofbase polyester and polyester segments in the composition is about 0.5 toabout 10 wt.-%, in particular about 0.7 to about 5 wt.-%, or about 0.5to about 1.5 wt.-%, or about 1 to about 2.5 wt.-%.

It is particularly advantageous that the polyether segments in thecopolyester-ether have a number-average molecular weight of from about600 to about 2000 g/mol, in particular about 800 to about 1600 g/mol,that the copolyester-ether contains one or more polyether segments in anamount of about 15 to about 35 wt.-%, in particular about 20 to about 30wt.-%, and that the amount of the copolyester-ether is selected withinthe range of about 0.5 to about 40 wt.-%, in relation to the finalcomposition, so that the amount of polyether segments to the totalamount of base polyester and polyester segments in the composition isabout 0.5 to about 10 wt.-%, in particular about 0.7 to about 5 wt.-%,or about 0.5 to about 1.5 wt.-%, or about 1 to about 2.5 wt.-%.

It is particularly advantageous that the polyether segments in thecopolyester-ether are selected from a linear or branched poly(propyleneglycol) or a linear or branched poly(butylene glycol) having anumber-average molecular weight of from about 600 to about 2000 g/mol,in particular about 800 to about 1600 g/mol, that the copolyester-ethercontains one or more polyether segments in an amount of about 15 toabout 35 wt.-%, in particular about 20 to about 30 wt.-%, and that theamount of the copolyester-ether is selected within the range of about0.5 to about 20 wt.-%, in relation to the final composition, so that theamount of polyether segments to the total amount of base polyester andpolyester segments in the composition is about 0.5 to about 10 wt.-%, inparticular about 0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-%,or about 1 to about 2.5 wt.-%.

The HALS used in the embodiments of the present invention is representedby the formula (I) or a mixture of compounds of formula (I),

wherein each R₁ independently represents C₁-C₄ alkyl, R₂ represents H,C₁-C₄ alkyl, OH, O—C₁-C₄ alkyl, or a further part of an oligomeric orpolymeric HALS, and R₃ represents a further part of a monomeric,oligomeric or polymeric HALS. For instance, when the HALS is a polymericHALS, R₃ may represent the polymer backbone of the polymeric HALS. Anexample of such as HALS is Uvinul® 5050. As a further example, whenadditionally R₂ represents a further part of an oligomeric or polymericHALS, the piperidine ring in above formula (I) is part of the repeatunit of the oligomeric or polymeric HALS. An example of such a HALS isUvinul® 5062. The HALS may be a mixture of compounds of formula (I). Anexample of such a HALS is Uvinul® 4092. Additionally or alternatively,the HALS may be as defined in paragraphs [0043] to [0046] of US2006/0058435 A1, which are incorporated herein by reference.

Specific HALS suitable for use in the invention are Uvinul® 4050,Uvinul® 4077, Uvinul® 4092, Uvinul® 5050 and Uvinul® 5062. Uvinul® 4050is particularly preferred. Alternatively, suitable HALS for theinvention are: Nylostab®, Hostavin®, and Nylostab® S-EED® from Clariant.

Advantageously, in the above formula (I) each R₁ independentlyrepresents C₁-C₄ alkyl, R₂ represents H or C₁-C₄ alkyl, or a furtherpart of an oligomeric or polymeric HALS.

It is particularly advantageous that in the above formula (I) each R₁represents methyl and R₂ represents H or methyl.

It is particularly advantageous that the HALS is a monomeric HALS.Preferably, the HALS has a molecular weight of about 400 g/mol or above,or about 400 to about 1500 g/mol, or about 400 to about 1200 g/mol, orin particular about 400 to about 800 g/mol.

It may also be particularly advantageous that the HALS is an oligomericor polymeric HALS. In those cases it may also be particularlyadvantageous that the HALS comprises one or more moieties of the formula(I),

wherein each R₁ independently represents C₁-C₄ alkyl, R₂ represents H orC₁-C₄ alkyl, and R₃ represents a further part of the oligomeric orpolymeric HALS. It may further be particularly advantageous in someembodiments that in the above formula (I), each R₁ represents methyl, R₂represents H or methyl, and R₃ represents a further part of theoligomeric or polymeric HALS.

When referring throughout the specification to oligomeric or polymericHALS, this is to be understood as referring to 2 to 8 repeating units incase of an oligomeric HALS and more than 8 repeating units in case of apolymeric HALS.

In some embodiments of the present invention, it may be particularlyadvantageous that the HALS is used in an amount of about 20 to about2500 ppm, or about 30 to about 2000 ppm, or about 40 to about 1000 ppm,and in particular about 50 to about 800 ppm, respective to the weight ofthe total composition. In the masterbatch embodiments, the amount ofHALS may be substantially higher, for instance about 250 to about 10,000ppm, or about 750 to about 10,000 ppm, or in particular about 1000 toabout 5000 ppm, respective to the weight of the total masterbatch.

In some embodiments of the present invention, it may be particularlyadvantageous that the polyether segments in the copolyester-ether have anumber-average molecular weight of from about 600 to about 2000 g/mol,in particular about 800 to about 1600 g/mol, that the copolyester-ethercontains one or more polyether segments in an amount of about 15 toabout 35 wt.-%, in particular about 20 to about 30 wt.-%, and that theamount of the copolyester-ether is selected within the range of about0.5 to about 20 wt.-%, in relation to the final composition, so that theamount of polyether segments to the total amount of base polyester andpolyester segments in the composition is about 0.5 to about 10 wt.-%, inparticular about 0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-%,or about 1 to about 2.5 wt.-%; and that HALS is represented by theformula (I) or a mixture of compounds of formula (I),

wherein each R₁ independently represents C₁-C₄ alkyl, in particularmethyl, R₂ represents H or C₁-C₄ alkyl, in particular H, and R₃represents a further part of a monomeric, oligomeric or polymeric HALS.

In some embodiments of the present invention, it may be particularlyadvantageous that the polyether segments in the copolyester-ether areselected from a linear or branched poly(propylene glycol) or a linear orbranched poly(butylene glycol) having a number-average molecular weightof from about 600 to about 2000 g/mol, in particular about 800 to about1600 g/mol, that the copolyester-ether contains one or more polyethersegments in an amount of about 15 to about 35 wt.-%, in particular about20 to about 30 wt.-%, and that the amount of the copolyester-ether isselected within the range of about 0.5 to about 20 wt.-%, in relation tothe final composition, so that the amount of polyether segments to thetotal amount of base polyester and polyester segments in the compositionis about 0.5 to about 10 wt.-%, in particular about 0.7 to about 5wt.-%, or about 0.5 to about 1.5 wt.-%, or about 1 to about 2.5 wt.-%;and that the HALS is represented by the formula (I) or a mixture ofcompounds of formula (I),

wherein each R₁ independently represents C₁-C₄ alkyl, in particularmethyl, R₂ represents H or C₁-C₄ alkyl, in particular H, and R₃represents a further part of a monomeric, oligomeric or polymeric HALS.

It may be particularly advantageous that the copolyester-ether and/orthe polyester is produced using a titanium-based polycondensationcatalyst. In particular, it may be advantageous that the polyester isproduced using a titanium-based polycondensation catalyst.

It may be particularly advantageous that the weight ratio of titaniummetal to HALS compound is about 1:2 to about 1:500, or about 1:10 toabout 1:250, in particular about 1:50 to about 1:200 in the finalcomposition.

Where the invention may further comprise a transition metal-basedoxidation catalyst, suitable oxidation catalysts include thosetransition metal catalysts that activate or promote the oxidation of thecopolyester-ether by ambient oxygen. Examples of suitable transitionmetals may include compounds comprising cobalt, manganese, copper,chromium, zinc, iron, or nickel. The transition metal-based oxidationcatalyst may be introduced into the composition in the form of a metalsalt. In this case, suitable counter ions for the transition metalinclude, but are not limited to, carboxylates, such as neodecanoates,octanoates, stearates, acetates, naphthalates, lactates, maleates,acetylacetonates, linoleates, oleates, palminates or 2-ethyl hexanoates,oxides, carbonates, chlorides, dioxides, hydroxides, nitrates,phosphates, sulfates, silicates or mixtures thereof. It is also possiblethat the transition metal-based oxidation catalyst is incorporated inthe polymer matrix during e.g. extrusion. The transition metal-basedoxidation catalyst can be added during polymerization of the polyesteror compounded into a suitable polyester thereby forming apolyester-based masterbatch that can be added during the preparation ofthe article. The cobalt compound may be physically separate from thecopolyester-ether, for example a sheath core or side-by-siderelationship, so as not to activate the copolyester-ether prior to meltblending into a preform or bottle.

Advantageously, the transition metal based oxidation catalyst is acobalt compound. In the container- or preform-related embodiments of thepresent invention, it may be advantageous that the transitionmetal-based oxidation catalyst is a cobalt compound that is present inan amount of about 40 to about 200 ppm, more specifically about 60 toabout 120 ppm, on basis of the weight of cobalt in the totalcomposition. Alternatively, it may be advantageous that the transitionmetal-based oxidation catalyst is a cobalt compound that is present inan amount of about 40 to about 250 ppm, more specifically about 60 toabout 200 ppm, on basis of the weight of cobalt in the totalcomposition. In the masterbatch-related embodiments of the presentinvention, it may be advantageous that the transition metal-basedoxidation catalyst is a cobalt compound that is present in an amount ofabout 50 to about 5,000 ppm, more specifically about 100 to about 2,500ppm, on basis of the weight of cobalt in the total composition. In theembodiments of the present invention, it may be advantageous that thetransition metal-based oxidation catalyst is a cobalt salt, inparticular a cobalt carboxylate, and especially a cobalt C₈-C₂₀carboxylate.

Advantageously, the weight ratio of metal of the transition metal basedoxidation catalyst to HALS compound is about 100:1 to about 1:50 orabout 75:1 to about 1:30 in particular about 50:1 to about 1:25,respective to the final composition.

In some embodiments of the present invention, it may be particularlyadvantageous that the polyether segments in the copolyester-ether areselected from a linear or branched poly(propylene glycol) or a linear orbranched poly(butylene glycol) having a number-average molecular weightof from about 600 to about 2000 g/mol, in particular about 800 to about1600 g/mol, that the copolyester-ether contains one or more polyethersegments in an amount of about 15 to about 35 wt.-%, in particular about20 to about 30 wt.-%, and that the amount of the copolyester-ether isselected within the range of about 0.5 to about 20 wt.-%, in relation tothe final composition, so that the amount of polyether segments to thetotal amount of base polyester and polyester segments in the compositionis about 0.5 to about 10 wt.-%, in particular about 0.7 to about 5wt.-%, or about 0.5 to 1.5 wt.-%, or about 1 to about 2.5 wt.-%. TheHALS in this embodiment is represented by the formula (I) or a mixtureof compounds of formula (I),

wherein each R₁ independently represents C₁-C₄ alkyl, in particularmethyl, R₂ represents H or C₁-C₄ alkyl, in particular H, and R₃represents a further part of a monomeric, oligomeric or polymeric HALS.The transition metal-based oxidation catalyst in this embodiment is acobalt compound, in particular a cobalt carboxylate, and especially acobalt C₈-C₂₀ carboxylate.

Embodiments in some aspects of the invention may further comprise afurther antioxidant selected from the group consisting of hinderedphenols, benzophenones, sulfur-based antioxidants, and phosphites.Examples of such antioxidants include, but are not limited to1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene(CAS: 1709-70-2),tetrakis(2,4-di-tert-butylphenyl)-1,1-biphenyl-4,4′-diylbisphosphonite(CAS: 38613-77-3) or pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (CAS:6683-19-8). Advantageously, one or more antioxidants are used in amountsof about 100 ppm to about 10,000 ppm, more specifically about 200 ppm toabout 5,000 ppm or about 300 ppm to about 3,000 ppm, and in particularabout 400 ppm to about 2,000 ppm, on basis of the total weight of theantioxidant to the total weight of the polyether composition.

Embodiments in some aspects of the invention may further compriseadditives selected from the group consisting of dyes, pigments, fillers,branching agents, reheat agents, anti-blocking agents, anti-staticagents, biocides, blowing agents, coupling agents, flame retardants,heat stabilizers, impact modifiers, crystallization aids, lubricants,plasticizers, processing aids, buffers, and slip agents. Representativeexamples of such additives are well-known to the skilled person.

It may be advantageous that an ionic compatibilizer is present or used.Suitable ionic compatibilizers can for instance be copolyesters preparedby using ionic monomer units as disclosed in WO 2011/031929 A2, page 5,incorporated herein by reference.

In the masterbatch embodiments of the present invention, it may beadvantageous that the masterbatch is mixed or packaged with anothermasterbatch comprising the transition metal based oxidation catalyst (a“salt and pepper” mixture). It may be advantageous that the othermasterbatch comprising the transition metal based oxidation catalystfurther comprises a polyester.

In another aspect of the invention, there is provided a“salt-and-pepper” mixture of masterbatches, more specifically akit-of-parts for use in preparing articles, preforms or containerscomprising two masterbatches which may optionally be in admixture:

a first masterbatch comprising:

-   -   a) a polyester as the predominant masterbatch component, and    -   b) a transition metal-based oxidation catalyst, wherein the        transition metal is selected from cobalt, manganese, copper,        chromium, zinc, iron, and nickel; and a second masterbatch        comprising:    -   d) a copolyester-ether as the predominant masterbatch component;        and    -   e) a HALS, preferably one of formula (I),

wherein each R₁ independently represents C₁-C₄ alkyl, in particularmethyl, R₂ represents H or C₁-C₄ alkyl, in particular H, and R₃represents a further part of a monomeric, oligomeric or polymeric HALS.

By “predominant masterbatch component” it is meant that the referred tocomponent is present in the masterbatch in more than 50 wt.-%, inparticular more than 80 wt.-%, more specifically more than 90 wt.-%.

The above kit-of-part or “salt-and-pepper” mixture is intended to beadded to a polyester base resin, i.e. the “salt-and-pepper” mixtureserves as a concentrate for introducing transition metal-based oxidationcatalyst, the copolyester-ether, and the HALS into the polyester baseresin.

In another aspect is provided a kit-of-parts for use in preparingarticles, preforms or containers comprising two masterbatches which mayoptionally be in admixture, wherein the second of the two masterbatchesis the masterbatch comprising copolyester-ether as described supra andinfra. In some embodiments, the first for the two masterbatchescomprises:

-   -   a) a polyester as the predominant masterbatch component, and    -   b) a transition metal-based oxidation catalyst, wherein the        transition metal is selected from cobalt, manganese, copper,        chromium, zinc, iron, and nickel.        In some embodiments, the polyester in the first masterbatch is        polyethylene terephthalate (PET). In some embodiments, the        transition metal-based oxidation catalyst is a cobalt compound.        In some embodiments, the cobalt compound is a cobalt C₈-C₂₀        carboxylate.

In this aspect of the invention, it may be particularly advantageousthat the polyether segments in the copolyester-ether are selected from alinear or branched poly(propylene glycol) or a linear or branchedpoly(butylene glycol) having a number-average molecular weight of fromabout 600 to about 2000 g/mol, in particular about 800 to about 1600g/mol, that the copolyester-ether contains one or more polyethersegments in an amount of about 15 to about 45 wt.-%, in particular about20 to about 40 wt.-%, and that the transition metal-based oxidationcatalyst is a cobalt compound, in particular a cobalt carboxylate, andespecially a cobalt C₈-C₂₀ carboxylate.

It may also be advantageous that the transition metal-based oxidationcatalyst is present in amounts of 1000 to 15000 ppm in the firstmasterbatch, in particular 2000 to 8000 ppm, and more specifically 3000to 6000 ppm.

It may also be advantageous that the HALS is present in an amount of100-30,000 ppm, on basis of the weight of the stabilizer in the secondmasterbatch, in particular 500 to 20,000 ppm, and more specifically 1000to 10000 ppm.

It may also be advantageous that the copolyester-ether and/or thepolyester is produced using a titanium compound, in particular atitanium-based polycondensation catalyst. The titanium-based compound isadvantageously present in amount of 2 to 500 ppm Ti, in particular 3 to400 ppm, more specifically 4 to 200 ppm, or 5 to 50 ppm, on basis of therespective copolyester-ether and/or the polyester masterbatch.

Advantageously, the polyester is selected from polyethyleneterephthalate, polyethylene naphthalate, polyethylene isophthalate,copolymers of polyethylene terephthalate, copolymers of polyethylenenaphthalate, copolymers of polyethylene isophthalate, or mixturesthereof; for example the polyester can be a copolymer of polyethyleneterephthalate, such as poly(ethylene terephthalate-co-ethyleneisophthalate) or poly(ethylene terephthalate-co-ethylene5-sulfoisophthalate). Advantageously, the polyester has an intrinsicviscosity, measured according to the method described in the TestProcedures below, of about 0.6 dl/g to about 1.1 dl/g, in particularabout 0.65 dl/g to about 0.95 dl/g.

The disclosed compositions, masterbatches and methods may be used forpreparing articles of manufacture. Suitable articles include, but arenot limited to, film, sheet, tubing, pipes, fiber, container preforms,blow molded articles such as rigid containers, thermoformed articles,flexible bags and the like and combinations thereof. Typical rigid orsemi-rigid articles can be formed from plastic, paper or cardboardcartons or bottles such as juice, milk, soft drink, beer and soupcontainers, thermoformed trays or cups. In addition, the walls of sucharticles may comprise multiple layers of materials.

Second Aspect

The composition for preparing an article, preform or container comprises80-99.5 parts by weight of a base polyester, including 85-99.5, 90-99.5,or 95-99.5 parts by weight of the base polyester. Preferably, thecomposition comprises 90-99.5 parts by weight of the base polyester.

Generally, copolyester-ethers suitable for the present inventioncomprise one or more polyester segments and one or more polyethersegments. The polyether segments advantageously have a number-averagemolecular weight of from about 200 to about 5000 g/mol. Advantageously,the polyether segments of the copolyester-ether has a number-averagemolecular weight of from about 600 to about 2500 g/mol, morespecifically between about 800 to about 1800 g/mol or between about 1000to about 1600 g/mol.

The one or more polyether segments may be present in an amount of about5 to about 95 wt.-% of the copolyester-ether. Advantageously, thepolyether segments are present in an amount of about 5 to about 45wt.-%, or about 15 to about 45 wt.-%, more specifically about 10 toabout 40 wt.-%, or about 20 to about 40 wt.-%, or in particular about 25to about 35 wt.-% or about 25 to about 30 wt.-%, in all cases based onthe copolyester-ether.

Generally, copolyester-ethers suitable for the present inventioncomprise one or more polyether segments in amounts so that the weightratio of the one or more polyether segments to the total amount of basepolyester and polyester segments in the composition is about 0.2 toabout 10 wt.-%, more specifically about 0.5 to about 10 wt.-%, or inparticular about 0.7 to about 5 wt.-%, or 0.5 to 1.5 wt.-%, or about 1to about 2.5 wt.-%.

Advantageously, the polyether segment is a poly (C₂-C₆-alkylene glycol)segment. The C₂-C₆-alkylene glycol may be a linear or branched aliphaticC₂-C₆-moiety. Specific examples of such copolyester-ethers includepoly(ethylene glycol), linear or branched poly(propylene glycol), linearor branched poly(butylene glycol), linear or branched poly(pentyleneglycol), linear or branched poly(hexylene glycol) as well as mixed poly(C₂-C₆-alkylene glycols) obtained from two or more of the glycolicmonomers used in preparing the before-mentioned examples.Advantageously, the polyether segment is a linear or branchedpoly(propylene glycol) or a linear or branched poly(butylene glycol).

The copolyester-ethers suitable for the present invention also compriseone or more polyester segments. The type of polyester in these segmentsis not particularly limited and can be any of the above-referencedpolyesters. Advantageously, the copolyester-ether comprises apolyethylene terephthalate (co)polymer segment. Advantageously, thecopolyester-ether comprises a polyethylene terephthalate (co)polymersegment and a linear or branched poly(butylene glycol) segment.

The composition for preparing an article, preform or container comprises0.5-20 parts by weight of a copolyester-ether, including 0.5-15, 0.5-10,or 0.5-5 parts by weight of the copolyester-ether. Preferably, thecomposition comprises 1-5 parts by weight of the copolyester-ether.

Methods of preparing polyethers and copolyester-ethers are well known inthe art. For example, the copolyester-ether can be produced by esterinterchange with the dialkyl ester of a dicarboxylic acid. In the esterinterchange process dialkyl esters of dicarboxylic acids undergotransesterification with one or more glycols in the presence of acatalyst such as zinc acetate as described in WO 2010/096459 A2,incorporated herein by reference. A suitable amount of elemental zinc inthe copolyester-ether can be about 35 to about 100 ppm, for exampleabout 40 to about 80 ppm, by weight of the copolyester-ether. Thepoly(alkylene oxide) glycols replace part of these glycols in thesetransesterification processes. The poly(alkylene oxide) glycols can beadded with the starting raw materials or added aftertransesterification. In either case, the monomer and oligomer mixturecan be produced continuously in a series of one or more reactorsoperating at elevated temperature and pressures at one atmosphere orlesser. Alternatively, the monomer and oligomer mixture can be producedin one or more batch reactors. Suitable conditions for these reactionsare temperatures of from about 180° C. to 250° C. and pressures of fromabout 1 bar to 4 bar.

Next, the mixture of copolyester-ether monomer and oligomers undergoesmelt-phase polycondensation to produce a polymer. The polymer isproduced in a series of one or more reactors operating at elevatedtemperatures. To facilitate removal of excess glycols, water, and otherreaction products, the polycondensation reactors are run under a vacuum.Catalysts for the polycondensation reaction include compounds ofantimony, germanium, tin, titanium and/or aluminum. In some embodiments,it may be advantageous to use a titanium compound. A suitable amount ofelemental Ti can be about 5 to about 60 ppm, for example about 10 to 35ppm. Reaction conditions for polycondensation can include (i) atemperature less than about 290° C., or about 10° C. higher than themelting point of the copolyester-ether; and (ii) a pressure of less thanabout 0.01 bar, decreasing as polymerization proceeds. Thiscopolyester-ether can be produced continuously in a series of one ormore reactors operating at elevated temperature and pressures less thanone atmosphere. Alternatively this copolyester-ether can be produced inone or more batch reactors. The intrinsic viscosity after melt phasepolymerization can be in the range of about 0.5 dl/g to about 1.5 dl/g.Antioxidants and other additives can be added before and/or duringpolymerization to control the degradation of the polyester-ethersegments. Alternatively, the copolyester-ethers can be produced byreactive extrusion of the polyether with the polyester. In theabove-described methods of preparing the copolyester-ethers, it mayhappen that the polyether does not fully react with the polyester but ispartly present as an intimate blend of the polyester and polyether.Therefore, throughout the specification and embodiments, the referenceto a copolyester-ether comprising one or more polyester segments and oneor more polyether segments is to be understood as referring to therespective copolyester-ethers, blends of respective polyesters andpolyethers, and mixtures comprising both the respectivecopolyester-ethers and blends of the respective polyesters andpolyethers.

The copolyester-ether is preferably used in amounts of about 0.5 toabout 20 wt.-% in relation to the final composition. Advantageously, theamount of the copolyester-ether is selected within the range of about0.5 to about 20 wt.-%, in relation to the final container, preform orarticle composition, so that the amount of polyether segments to thetotal amount of base polyester and polyester segments in the compositionis about 0.2 to about 10 wt.-%, more specifically about 0.5 to about 10wt.-%, or in particular about 0.7 to about 5 wt.-%, or about 0.5 toabout 1.5 wt.-% or about 1 to about 2.5 wt.-%.

It is particularly advantageous that the copolyester-ether contains oneor more polyether segments in an amount of about 5 to about 45 wt.-%, inparticular about 15 to about 35 wt.-%, more specifically about 20 toabout 30 wt.-%, and that the amount of the copolyester-ether is selectedso that the amount of polyether segments to the total amount of basepolyester and polyester segments in the composition is about 0.5 toabout 10 wt.-%, in particular about 0.7 to about 5 wt.-%, or about 0.5to about 1.5 wt.-%, or about 1 to about 2.5 wt. %.

It is particularly advantageous that the polyether segments in thecopolyester-ether have a number-average molecular weight of from about600 to about 2500 g/mol, in particular about 800 to about 1600 g/mol,that the copolyester-ether contains one or more polyether segments in anamount of about 15 to about 35 wt.-%, in particular about 20 to about 30wt.-%, and that the amount of the copolyester-ether is selected withinthe range of about 0.5 to about 20 wt.-%, in relation to the finalcomposition, so that the amount of polyether segments to the totalamount of base polyester and polyester segments in the composition isabout 0.5 to about 10 wt.-%, in particular about 0.7 to about 5 wt.-%,or about 0.5 to about 1.5 wt.-%, or about 1 to about 2.5 wt.-%.

It is particularly advantageous that the polyether segments in thecopolyester-ether are selected from a linear or branched poly(propyleneglycol) or a linear or branched poly(butylene glycol) having anumber-average molecular weight of from about 600 to about 2500 g/mol,in particular about 800 to about 1600 g/mol, that the copolyester-ethercontains one or more polyether segments in an amount of about 15 toabout 35 wt.-%, in particular about 20 to about 30 wt.-%, and that theamount of the copolyester-ether is selected within the range of about0.5 to about 20 wt.-%, in relation to the final composition, so that theamount of polyether segments to the total amount of base polyester andpolyester segments in the composition is about 0.5 to about 10 wt.-%, inparticular about 0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-%,or about 1 to about 2.5 wt.-%.

Advantageously, the copolyester-ether and/or the polyester is producedusing a titanium-based polycondensation and/or transesterficationcatalyst. In particular, it may be advantageous that the polyester isproduced using a titanium-based polycondensation catalyst.

The compositions, kit-of-parts and processes of the invention furtherutilize a transition metal-based oxidation catalyst selected from acobalt, manganese, copper, chromium, zinc, iron, or nickel compound. Thetransition metal-based oxidation catalyst may be present in the form ofa metal salt. In this case, suitable counter ions for the transitionmetal include, but are not limited to, carboxylates, such asneodecanoates, octanoates, stearates, acetates, naphthalates, lactates,maleates, acetylacetonates, linoleates, oleates, palminates or 2-ethylhexanoates, oxides, carbonates, chlorides, dioxides, hydroxides,nitrates, phosphates, sulfates, silicates or mixtures thereof. It isparticularly advantageous to utilize a cobalt-based oxidation catalyst.Examples include cobalt carboxylates and sulfonates.

In some embodiments, the weight ratio of the transition metal-basedoxidation catalyst to the titanium compound, on the basis of the weightof the transition metal and the titanium, is from 50:1 to 1:1.Optionally, the ratio is from 25:1 to 1:1, 10:1 to 1:1, 5:1 to 1:1 or2:1 to 1:1.

Advantageously, the titanium compound is present in an amount of about 5to about 20 ppm, more specifically about 5 to about 15 ppm, and inparticular about 5 to about 10 ppm, on basis of the weight of titaniumin the total composition, and that the transition metal based oxidationcatalyst is present in an amount of 30 to 200 ppm, more specificallyabout 50 to about 150 ppm, and in particular about 75 to about 125 ppm,on basis of the weight of the transition metal in the total composition.

It may be particularly advantageous that titanium compound is apolycondensation and/or transesterfication catalyst.

Advantageously, the polyether segments in the copolyester-ether have anumber-average molecular weight of from about 600 to about 2500 g/mol,in particular about 800 to about 1600 g/mol, that the polyether segmentis a linear or branched poly (C₂-C₆-alkylene glycol) segment, that thetransition metal-based oxidation catalyst is a cobalt compound, that thetitanium compound is present in an amount of about 5 to about 20 ppm, onbasis of the weight of the titanium in the total composition, and thatthe transition metal based oxidation catalyst is present in an amount ofabout 30 to about 200 ppm, on basis of the weight of the transitionmetal in the total composition.

Advantageously, the polyether segments in the copolyester-ether have anumber-average molecular weight of from about 600 to about 2500 g/mol,in particular about 800 to about 1600 g/mol, that the polyether segmentis a linear or branched poly (C₂-C₆-alkylene glycol) segment, that thetransition metal-based oxidation catalyst is a cobalt compound, that thetitanium compound is a polycondensation and/or transesterficationcatalyst, that the titanium compound is present in an amount of about 5to about 20 ppm, in particular about 7 to about 15 ppm, on basis of theweight of titanium in the total composition, and that the transitionmetal based oxidation catalyst is present in an amount of about 30 toabout 200 ppm, in particular 50 to about 150 ppm, on basis of the weightof the transition metal in the total composition.

In the kit-of-parts embodiments of the present invention, it may beadvantageous that the kit-of-parts is packaged for storage. In thekit-of-parts embodiments of the present invention, it may beadvantageous that the polyester is a polyethylene terephthalate(co)polyester. In the kit-of-parts embodiments of the present invention,it may be advantageous that the copolyester-ether comprises one or morepolyether segments having a number-average molecular weight of fromabout 200 to about 5000 g/mol and is a linear or branched poly(C₂-C₆-alkylene glycol) segment.

In the kit-of-parts embodiments of the present invention, it may beadvantageous that in the first masterbatch the transition metal basedoxidation catalyst is present in an amount of about 500 to about 15000ppm, in particular about 750 to about 10000 ppm, or about 1000 to about5000 ppm, on basis of the weight of the transition metal in firstmasterbatch. In the kit-of-parts embodiments of the present invention,it may be advantageous that the weight ratio of the transitionmetal-based oxidation catalyst to the titanium compound present in thefirst masterbatch, on basis of the weight of the transition metal andthe titanium, is from about 5:1 to about 500:1, more specifically about7:1 to about 400:1, in particular about 10:1 to about 250:1 or about20:1 to about 150:1.

In the kit-of-parts embodiments of the present invention, it may beparticularly advantageous that transition metal-based oxidation catalystis a cobalt compound that is present in an amount of about 500 to about15000 ppm, in particular about 750 to about 10000 ppm, more specificallyabout 1000 to about 5000 ppm, on basis of the weight of cobalt in thefirst masterbatch and that the titanium compound is present in an amountof about 5 to about 500 ppm, in particular about 7 to about 300 ppm,more specifically about 10 to about 200 ppm, even more specificallyabout 20 to about 150 ppm, or about 50 to about 100 ppm, on basis of theweight of the titanium in the first masterbatch.

In the kit-of-parts embodiments of the present invention, it may beadvantageous that the second masterbatch comprises a titanium compound,e.g. in the form of a polycondensation and/or transesterficationcatalyst. In some embodiments, this may reduce unwanted side-products.

Embodiments in some aspects of the invention may further comprise anantioxidant, in particular one selected from the group consisting ofhindered amine light stabilizers (HALS), hindered phenols,benzophenones, sulfur-based antioxidants, and phosphites. Examples ofsuch antioxidants include, but are not limited to1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene(CAS: 1709-70-2),tetrakis(2,4-di-tert-butylphenyl)-1,1-biphenyl-4,4′-diylbisphosphonite(CAS: 38613-77-3) or pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (CAS:6683-19-8). Advantageously, one or more antioxidants are used in a totalamount of about 100 ppm to about 10,000 ppm, more specifically about 200ppm to about 5,000 ppm or about 300 ppm to about 3,000 ppm, and inparticular about 500 ppm to about 2,500 ppm, on basis of the totalweight of the antioxidant to the total weight of the composition.

Embodiments in some aspects of the invention may further compriseadditives selected from the group consisting of dyes, pigments, fillers,branching agents, reheat agents, anti-blocking agents, anti-staticagents, biocides, blowing agents, coupling agents, flame retardants,heat stabilizers, impact modifiers, crystallization aids, lubricants,plasticizers, processing aids, buffers, and slip agents. Representativeexamples of such additives are well-known to the skilled person.

It may be advantageous that an ionic compatibilizer is present or used.Suitable ionic compatibilizers can for instance be copolyesters preparedby using ionic monomer units as disclosed in WO 2011/031929 A2, page 5,incorporated herein by reference.

The disclosed compositions, kit-of-parts and methods may be used forpreparing various articles of manufacture. Suitable articles include,but are not limited to, film, sheet, tubing, pipes, fiber, containerpreforms, blow molded articles such as rigid containers, thermoformedarticles, flexible bags and the like and combinations thereof. Typicalrigid or semi-rigid articles can be formed from plastic, paper orcardboard cartons or bottles such as juice, milk, soft drink, beer andsoup containers, thermoformed trays or cups. In addition, the walls ofsuch articles may comprise multiple layers of materials.

Third Aspect

The composition for preparing an article, preform or container comprises80-99.5 parts by weight of a base polyester, including 85-99.5, 90-99.5,or 95-99.5 parts by weight of the base polyester. Preferably, thecomposition comprises 90-99.5 parts by weight of the base polyester.

Generally, copolyester-ethers suitable for the present inventioncomprise one or more polyester segments and one or more polyethersegments having a number-average molecular weight of from about 200 toabout 5000 g/mol. Advantageously, the copolyester-ether has anumber-average molecular weight of from about 600 to about 2500 g/mol,more specifically about 800 to about 1800 g/mol or about 1000 to about1600 g/mol.

The one or more polyether segments may advantageously be present in anamount of about 5 to about 45 wt.-% or about 15 to about 45 wt.-% of thecopolyester-ether. Advantageously, the polyether segments are present inan amount of about 10 to about 40 wt.-%, more specifically about 20 toabout 40 wt.-%, or in particular about 25 to about 35 wt.-% or about 25to about 30 wt.-%, in all cases based on the copolyester-ether.

Generally, copolyester-ethers suitable for the present inventioncomprise one or more polyether segments in amounts so that the weightratio of the one or more polyether segments to the total amount of basepolyester and polyester segments in the composition is about 0.2 toabout 10 wt.-%, more specifically about 0.5 to about 10 wt.-%, or inparticular about 0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-%,or about 1 to about 2.5 wt.-%.

Advantageously, the polyether segment is a poly (C₂-C₆-alkylene glycol)segment. The C₂-C₆-alkylene glycol may be a linear or branched aliphaticC₂-C₆-moiety. Specific examples of such copolyester-ethers includepoly(ethylene glycol), linear or branched poly(propylene glycol), linearor branched poly(butylene glycol) glycol, linear or branchedpoly(pentylene glycol), linear or branched poly(hexylene glycol) as wellas mixed poly (C₂-C₆-alkylene glycols) obtained from two or more of theglycolic monomers used in preparing the before-mentioned examples.Advantageously, the polyether segment is a linear or branchedpoly(propylene glycol) or a linear or branched poly(butylene glycol).

The copolyester-ethers suitable for the present invention also compriseone or more polyester segments. The type of polyester in these segmentsis not particularly limited and can be any of the above-referencedpolyesters. Advantageously, the copolyester-ether comprises apolyethylene terephthalate (co)polymer segment. Advantageously, thecopolyester-ether comprises a polyethylene terephthalate (co)polymersegment and a linear or branched poly(butylene glycol) segment.

The composition for preparing an article, preform or container comprises0.5-20 parts by weight of a copolyester-ether, in particular 0.5-15,0.5-10, or 0.5-5 parts by weight of the copolyester-ether. Preferably,the composition comprises 1-5 parts by weight of the copolyester-ether.

Methods of preparing polyethers and copolyester-ethers are well known inthe art. For example, the copolyester-ether can be produced by esterinterchange with the dialkyl ester of a dicarboxylic acid. In the esterinterchange process dialkyl esters of dicarboxylic acids undergotransesterification with one or more glycols in the presence of acatalyst such as zinc acetate as described in WO 2010/096459 A2,incorporated herein by reference. A suitable amount of elemental zinc inthe copolyester-ether can be about 35 to about 100 ppm, for exampleabout 40 to about 80 ppm, by weight of the copolyester-ether. Thepoly(alkylene oxide) glycols replace part of these glycols in thesetransesterification processes. The poly(alkylene oxide) glycols can beadded with the starting raw materials or added aftertransesterification. In either case, the monomer and oligomer mixturecan be produced continuously in a series of one or more reactorsoperating at elevated temperature and pressures at one atmosphere orlesser. Alternatively, the monomer and oligomer mixture can be producedin one or more batch reactors. Suitable conditions for these reactionsare temperatures of from about 180° C. to 250° C. and pressures of fromabout 1 bar to 4 bar.

Next, the mixture of copolyester-ether monomer and oligomers undergoesmelt-phase polycondensation to produce a polymer. The polymer isproduced in a series of one or more reactors operating at elevatedtemperatures. To facilitate removal of excess glycols, water, and otherreaction products, the polycondensation reactors are run under a vacuum.Catalysts for the polycondensation reaction include compounds ofantimony, germanium, tin, titanium and/or aluminum. In some embodiments,it may be advantageous to use a titanium compound. A suitable amount ofelemental Ti can be about 5 to about 60 ppm, for example about 10 to 35ppm. Reaction conditions for polycondensation can include (i) atemperature less than about 290° C., or about 10° C. higher than themelting point of the copolyester-ether; and (ii) a pressure of less thanabout 0.01 bar, decreasing as polymerization proceeds. Thiscopolyester-ether can be produced continuously in a series of one ormore reactors operating at elevated temperature and pressures less thanone atmosphere. Alternatively this copolyester-ether can be produced inone or more batch reactors. The intrinsic viscosity after melt phasepolymerization can be in the range of about 0.5 dl/g to about 1.5 dl/g.Antioxidants and other additives can be added before and/or duringpolymerization to control the degradation of the polyester-ethersegments. Alternatively, the copolyester-ethers can be produced byreactive extrusion of the polyether with the polyester. In theabove-described methods of preparing the copolyester-ethers, it mayhappen that the polyether does not fully react with the polyester but ispartly present as an intimate blend of the polyester and polyether.Therefore, throughout the specification and embodiments, the referenceto a copolyester-ether comprising one or more polyester segments and oneor more polyether segments is to be understood as referring to therespective copolyester-ethers, blends of respective polyesters andpolyethers, and mixtures comprising both the respectivecopolyester-ethers and blends of the respective polyesters andpolyethers.

The copolyester-ether is preferably used in amounts of about 0.5 toabout 20 wt.-% in relation to the final composition. Advantageously, theamount of the copolyester-ether is selected within the range of about0.5 to about 20 wt.-%, in relation to the final container, preform andarticle composition, so that the amount of polyether segments to thetotal amount of base polyester and polyester segments in the compositionis about 0.2 to about 10 wt.-%, more specifically about 0.5 to about 10wt.-%, or in particular about 0.7 to about 5 wt.-%, or about 0.5 toabout 1.5 wt.-%, or about 1 to about 2.5 wt.-%.

It is particularly advantageous that the copolyester-ether contains oneor more polyether segments in an amount of about 5 to about 45 wt.-%, inparticular about 15 to about 35 wt.-%, more specifically about 20 toabout 30 wt.-%, and that the amount of the copolyester-ether is selectedso that the amount of polyether segments to the total amount of basepolyester and polyester segments in the composition is about 0.5 toabout 10 wt.-%, in particular about 0.7 to about 5 wt.-%, or about 0.5to about 1.5 wt.-%, or about 1 to about 2.5 wt.-%.

It is particularly advantageous that the polyether segments in thecopolyester-ether have a number-average molecular weight of from about600 to about 2500 g/mol, in particular about 800 to about 1600 g/mol,that the copolyester-ether contains one or more polyether segments in anamount of about 15 to about 35 wt.-%, in particular about 20 to about 30wt.-%, and that the amount of the copolyester-ether is selected withinthe range of about 0.5 to about 40 wt.-%, in relation to the finalcomposition, so that the amount of polyether segments to the totalamount of base polyester and polyester segments in the composition isabout 0.5 to about 10 wt.-%, in particular about 0.7 to about 5 wt.-%,or about 0.5 to about 1.5 wt.-%, or about 1 to about 2.5 wt.-%.

Advantageously, the polyether segments in the copolyester-ether areselected from a linear or branched poly(propylene glycol) or a linear orbranched poly(butylene glycol) having a number-average molecular weightof from about 600 to about 2500 g/mol, in particular about 800 to about1600 g/mol, that the copolyester-ether contains one or more polyethersegments in an amount of about 15 to about 35 wt.-%, in particular about20 to about 30 wt.-%, and that the amount of the copolyester-ether isselected within the range of about 0.5 to about 20 wt.-%, in relation tothe final composition, so that the amount of polyether segments to thetotal amount of base polyester and polyester segments in the compositionis about 0.5 to about 10 wt.-%, in particular about 0.7 to about 5wt.-%, or about 0.5 to about 1.5 wt.-%, or about 1 to about 2.5 wt.-%.

Advantageously, the copolyester-ether and/or the polyester is producedusing a titanium-based polycondensation and/or transesterificationcatalyst. In particular, it may be advantageous that the polyester isproduced using a titanium-based polycondensation catalyst.

The compositions, masterbatches and processes of the invention furtherutilize a transition metal-based oxidation catalyst selected from acobalt, manganese, copper, chromium, zinc, iron, or nickel compound. Thetransition metal-based oxidation catalyst may be present in the form ofa metal salt. In this case, suitable counter ions for the transitionmetal include, but are not limited to, carboxylates, such asneodecanoates, octanoates, stearates, acetates, naphthalates, lactates,maleates, acetylacetonates, linoleates, oleates, palminates or 2-ethylhexanoates, oxides, borides, carbonates, chlorides, dioxides,hydroxides, nitrates, phosphates, sulfates, silicates or mixturesthereof. It is particularly advantageous to utilize a cobalt-basedoxidation catalyst. Examples include cobalt carboxylates and sulfonates.

Advantageously, the titanium compound is present in an amount of about 5to about 20 ppm, more specifically about 5 to about 15 ppm, and inparticular about 5 to about 10 ppm, on basis of the weight of titaniumin the total composition, and that the transition metal based oxidationcatalyst is present in an amount of 30 to 200 ppm, more specificallyabout 50 to about 150 ppm, and in particular about 75 to about 125 ppm,on basis of the weight of the transition metal in the total composition.

It may be particularly advantageous that titanium compound is apolycondensation and/or transesterfication catalyst.

Advantageously, the polyether segments in the copolyester-ether have anumber-average molecular weight of from about 600 to about 2500 g/mol,in particular about 800 to about 1600 g/mol, that the polyether segmentis a linear or branched poly (C₂-C₆-alkylene glycol) segment, that thepolyether segments are present in the copolyester-ether in an amount ofabout 10 to about 40 wt.-%, in particular about 20 to about 35 wt.-%,that the transition metal-based oxidation catalyst is a cobalt compound,and that the transition metal based oxidation catalyst is present in anamount of about 30 to about 300 ppm, on basis of the weight of thetransition metal in the total composition.

Advantageously, the polyether segments in the copolyester-ether have anumber-average molecular weight of from about 600 to about 2500 g/mol,in particular about 800 to about 1600 g/mol, that the polyether segmentis a linear or branched poly (C₂-C₆-alkylene glycol) segment, that thepolyether segments are present in the copolyester-ether in an amount ofabout 10 to about 40 wt.-%, in particular about 20 to about 35 wt.-%,that the transition metal-based oxidation catalyst is a cobalt compound,and that the transition metal based oxidation catalyst is present in anamount of about 30 to about 200 ppm, in particular 50 to 150 ppm, onbasis of the weight of the transition metal in the total composition.

In the kit-of-parts embodiments of the present invention, it may beadvantageous that the kit-of-parts is packaged for storage. In thekit-of-parts embodiments of the present invention, it may beadvantageous that the polyester is a polyethylene terephthalate(co)polyester. In the kit-of-parts embodiments of the present invention,it may be advantageous that the copolyester-ether comprises one or morepolyether segments having a number-average molecular weight of fromabout 600 to about 2500 g/mol and are linear or branched poly(C₂-C₆-alkylene glycol) segments.

In the kit-of-parts embodiments of the present invention, it may beadvantageous that in the first masterbatch the transition metal basedoxidation catalyst is present in an amount of about 500 to about 15000ppm, in particular about 750 to about 10000 ppm, or about 1000 to 5000ppm on basis of the weight of the transition metal in first masterbatch.In the kit-of-parts embodiments of the present invention, it may beadvantageous that the weight ratio of the transition metal-basedoxidation catalyst to the titanium compound present in the firstmasterbatch, on basis of the weight of the transition metal and thetitanium, is from about 5:1 to about 500:1, more specifically about 7:1to 400:1, in particular about 10:1 to 250:1 or about 20:1 to about150:1.

In the kit-of-parts embodiments of the present invention, it may beparticularly advantageous that transition metal-based oxidation catalystis a cobalt compound that is present in an amount of about 500 to about15000 ppm, in particular about 750 to about 10000 ppm, more specificallyabout 1000 to about 5000 ppm on basis of the weight of cobalt in thefirst masterbatch, and that the titanium compound is present in anamount of about 5 to about 500 ppm, in particular about 7 to about 300ppm, more specifically about 10 to about 200 ppm, even more specificallyabout 20 to about 150 ppm, or about 50 to about 100 ppm, on basis of theweight of the titanium in the first masterbatch.

In the kit-of-parts embodiments of the present invention, it may beadvantageous that the second masterbatch comprises a titanium compound,e.g. in the form of a polycondensation and/or transesterficationcatalyst. In some embodiments, this may reduce unwanted side-products.

Embodiments in some aspects of the invention may further comprise anantioxidant selected from the group consisting of hindered amine lightstabilizers (HALS), hindered phenols, benzophenones, sulfur-basedantioxidants, and phosphites. Examples of such antioxidants include, butare not limited to1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene(CAS: 1709-70-2),tetrakis(2,4-di-tert-butylphenyl)-1,1-biphenyl-4,4′-diylbisphosphonite(CAS: 38613-77-3) or pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (CAS: 6683-19-8Advantageously, one or more antioxidants are used in a total amount ofabout 100 ppm to about 10,000 ppm, more specifically about 200 ppm toabout 5,000 ppm or about 300 ppm to about 3,000 ppm, and in particularabout 500 ppm to about 2,500 ppm, on basis of the total weight of theantioxidant to the total weight of the composition Embodiments in someaspects of the invention may further comprise additives selected fromthe group consisting of dyes, pigments, fillers, branching agents,reheat agents, anti-blocking agents, anti-static agents, biocides,blowing agents, coupling agents, flame retardants, heat stabilizers,impact modifiers, crystallization aids, lubricants, plasticizers,processing aids, buffers, and slip agents. Representative examples ofsuch additives are well-known to the skilled person.

It may be advantageous that an ionic compatibilizer is present or used.Suitable ionic compatibilizers can for instance be copolyesters preparedby using ionic monomer units as disclosed in WO 23011/031929 A2, page 5,incorporated herein by reference.

The disclosed compositions, masterbatches and methods may be used forpreparing articles of manufacture. Suitable articles include, but arenot limited to, film, sheet, tubing, pipes, fiber, container preforms,blow molded articles such as rigid containers, thermoformed articles,flexible bags and the like and combinations thereof. Typical rigid orsemi-rigid articles can be formed from plastic, paper or cardboardcartons or bottles such as juice, milk, soft drink, beer and soupcontainers, thermoformed trays or cups. In addition, the walls of sucharticles may comprise multiple layers of materials.

Fourth Aspect

Advantageously, the polyester is a polyethylene terephthalate or acopolymer thereof having a melting point, determined according to ASTM D3418-97, of about 240° C. to about 250° C., in particular about 242° C.to about 250° C., and especially about 245° C. to about 250° C.

Advantageously, the polyester used in preparing the articles of thepresent invention has an intrinsic viscosity, measured according to themethod described in the Test Procedures below, of about 0.6 dl/g toabout 1.1 dl/g, in particular about 0.65 dl/g to about 0.95 dl/g.

The composition for preparing an article, preform or container comprises80-99.5 parts by weight of a base polyester, including 85-99.5, 90-99.5,or 95-99.5 parts by weight of the base polyester. Preferably, thecomposition comprises 90-99.5 parts by weight of the base polyester.

Copolyester-ethers suitable for the present invention comprise one ormore polyester segments and one or more polyether segments having anumber-average molecular weight of from about 200 to about 5000 g/mol.Advantageously, the copolyester-ether has a number-average molecularweight of from about 600 to about 2500 g/mol, more specifically fromabout 800 to about 1800 g/mol or from about 1000 to about 1600 g/mol.The copolyester-ethers are present in the composition in an amount from0.5-20 parts by weight, including 0.5-15 parts by weight, 0.5-10 partsby weight, and 0.5-5 parts by weight. Preferably, the compositioncomprises 0.5-10 parts by weight of the copolyester-ethers.

The one or more polyether segments are present in an amount of about 5to about 45 wt.-% of the copolyester-ether. Advantageously, thepolyether segments are present in an amount of about 15 to about 45wt.-%, or about 10 to about 40 wt.-%, more specifically about 20 toabout 40 wt.-%, or in particular about 25 to about 35 wt.-% or about 25to about 30 wt.-%, in all cases based on the copolyester-ether.

Generally, copolyester-ethers suitable for the present inventioncomprise one or more polyether segments in amounts so that the weightratio of the one or more polyether segments to the total amount of basepolyester and polyester segments in the composition is about 0.2 toabout 10 wt.-%, more specifically about 0.5 to about 5 wt.-%, or inparticular about 0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-%,or about 1 to about 2.5 wt.-%.

Advantageously, the polyether segment is a poly (C₂-C₆-alkylene glycol)segment. The C₂-C₆-alkylene glycol may be a linear or branched aliphaticC₂-C₆-moiety. Specific examples of such copolyester-ethers includepoly(ethylene glycol), linear or branched poly(propylene glycol), linearor branched poly(butylene glycol), linear or branched poly(pentyleneglycol), linear or branched poly(hexylene glycol) as well as mixed poly(C₂-C₆-alkylene glycols) obtained from two or more of the glycolicmonomers used in preparing the before-mentioned examples.Advantageously, the polyether segment may be a linear or branchedpoly(propylene glycol) or a linear or branched poly(butylene glycol).

The copolyester-ethers suitable for the present invention also compriseone or more polyester segments. The type of polyester in these segmentsis not particularly limited and can be any of the above-referencedpolyesters. Advantageously, the copolyester-ether comprises apolyethylene terephthalate (co)polymer segment. Advantageously, thecopolyester-ether may comprise a polyethylene terephthalate (co)polymersegment and a linear or branched poly(butylene glycol) segment.

Furthermore, the melting point difference, determined according to ASTMD 3418-97, between the polyester and the copolyester-ether is less thanabout 15° C. Advantageously, the melting point difference is less thanabout 10° C., more specifically less than about 8° C. or less than about5° C. Advantageously, the melting point, determined according to ASTM D3418-97, of the polyester is about 240° C. to about 250° C. and that ofthe copolyester-ether is about 225° C. to 250° C., in particular about230° C. to about 250° C., especially about 232° C. to about 250° C. orabout 240° C. to about 250° C. The melting points of thecopolyester-ether and polyester may be determined for the startingmaterials or in the final composition.

Methods of preparing polyethers and copolyester-ethers are well known inthe art. For example, the copolyester-ether can be produced by esterinterchange with the dialkyl ester of a dicarboxylic acid. In the esterinterchange process dialkyl esters of dicarboxylic acids undergotransesterification with one or more glycols in the presence of acatalyst such as zinc acetate as described in WO 2010/096459 A2,incorporated herein by reference. A suitable amount of elemental zinc inthe copolyester-ether can be about 35 to about 100 ppm, for exampleabout 40 to about 80 ppm, by weight of the copolyester-ether. Thepoly(alkylene oxide) glycols replace part of these glycols in thesetransesterification processes. The poly(alkylene oxide) glycols can beadded with the starting raw materials or added aftertransesterification. In either case, the monomer and oligomer mixturecan be produced continuously in a series of one or more reactorsoperating at elevated temperature and pressures at one atmosphere orlesser. Alternatively, the monomer and oligomer mixture can be producedin one or more batch reactors. Suitable conditions for these reactionsare temperatures of from about 180° C. to 250° C. and pressures of fromabout 1 bar to 4 bar.

Next, the mixture of copolyester-ether monomer and oligomers undergoesmelt-phase polycondensation to produce a polymer. The polymer isproduced in a series of one or more reactors operating at elevatedtemperatures. To facilitate removal of excess glycols, water, and otherreaction products, the polycondensation reactors are run under a vacuum.Catalysts for the polycondensation reaction include compounds ofantimony, germanium, tin, titanium and/or aluminum. In some embodiments,it may be advantageous to use a titanium compound. A suitable amount ofelemental Ti can be about 5 to about 60 ppm, for example about 10 to 35ppm. Reaction conditions for polycondensation can include (i) atemperature less than about 290° C., or about 10° C. higher than themelting point of the copolyester-ether; and (ii) a pressure of less thanabout 0.01 bar, decreasing as polymerization proceeds. Thiscopolyester-ether can be produced continuously in a series of one ormore reactors operating at elevated temperature and pressures less thanone atmosphere. Alternatively this copolyester-ether can be produced inone or more batch reactors. The intrinsic viscosity after melt phasepolymerization can be in the range of about 0.5 dl/g to about 1.5 dl/g.Antioxidants and other additives can be added before and/or duringpolymerization to control the degradation of the polyester-ethersegments. Alternatively, the copolyester-ethers can be produced byreactive extrusion of the polyether with the polyester. In theabove-described methods of preparing the copolyester-ethers, it mayhappen that the polyether does not fully react with the polyester but ispartly present as an intimate blend of the polyester and polyether.Therefore, throughout the specification and embodiments, the referenceto a copolyester-ether comprising one or more polyester segments and oneor more polyether segments is to be understood as referring to therespective copolyester-ethers, blends of respective polyesters andpolyethers, and mixtures comprising both the respectivecopolyester-ethers and blends of the respective polyesters andpolyethers.

The melting point of the copolyester-ether can be convenientlycontrolled by adjusting various characteristics or parameters of thepolymer composition, as known to those skilled in the art. For instance,one skilled in the art may opt to suitably select the molecular weightof the polyether segment, and/or the weight ratio of polyester segmentto polyether segment to adjust the melting point. It is also possible toselect different types of polyester to adjust the melting point. Forexample, aromatic polyesters are known to have higher melting pointsthan aliphatic polyesters. Thus, one skilled in the art may select ormix suitable polyesters to reliably adjust the melting point of thecopolyester-ether. Other options include suitably selecting the type ofpolyether. For instance, the chain length and the presence or absence ofa side chain influences the melting point of the copolyester-ether. Afurther possibility is the addition of additives.

The copolyester-ether is preferably used in amounts of about 0.5 toabout 20 wt.-% in relation to the final composition. Advantageously, theamount of the copolyester-ether is selected within the range of about0.5 to about 10 wt.-%, in relation to the final composition, so that theamount of polyether segments to the total amount of base polyester andpolyester segments in the composition is about 0.2 to about 10 wt.-%,more specifically about 0.5 to about 10 wt.-%, or in particular about0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-%, or about 1 toabout 2.5 wt.-%.

It is particularly advantageous that the copolyester-ether contains oneor more polyether segments in an amount of about 15 to about 35 wt.-%,in particular about 20 to about 30 wt.-%, and that the amount of thecopolyester-ether is selected within the range of about 0.5 to about 20wt.-%, in relation to the final composition, so that the amount ofpolyether segments to the total amount of base polyester and polyestersegments in the composition is about 0.5 to about 10 wt.-%, inparticular about 0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-%,or about 1 to about 2.5 wt.-%.

It is particularly advantageous that the polyether segments in thecopolyester-ether have a number-average molecular weight of from about600 to about 2000 g/mol, in particular about 800 to about 1600 g/mol,that the copolyester-ether contains one or more polyether segments in anamount of about 15 to about 35 wt.-%, in particular about 20 to about 30wt.-%, and that the amount of the copolyester-ether is selected withinthe range of about 0.5 to about 20 wt.-%, in relation to the finalcomposition, so that the amount of polyether segments to the totalamount of base polyester and polyester segments in the composition isabout 0.5 to about 10 wt.-%, in particular about 0.7 to about 5 wt.-%,or about 0.5 to 1.5 wt.-%, or about 1 to about 2.5 wt.-%.

It is particularly advantageous that the polyether segments in thecopolyester-ether are selected from a linear or branched poly(propyleneglycol) or a linear or branched poly(butylene glycol) having anumber-average molecular weight of from about 600 to about 2000 g/mol,in particular about 800 to about 1600 g/mol, that the copolyester-ethercontains one or more polyether segments in an amount of about 15 toabout 35 wt.-%, in particular about 20 to about 30 wt.-%, and that theamount of the copolyester-ether is selected within the range of about0.5 to about 20 wt.-%, in relation to the final composition, so that theamount of polyether segments to the total amount of base polyester andpolyester segments in the composition is about 0.5 to about 10 wt.-%, inparticular about 0.7 to about 5 wt.-%, or 0.5 to 1.5 wt.-%, or about 1to about 2.5 wt.-%.

It is particularly advantageous that the polyether segments in thecopolyester-ether are selected from a linear or branched poly(propyleneglycol) or a linear or branched poly(butylene glycol) having anumber-average molecular weight of from about 600 to about 2000 g/mol,in particular about 800 to about 1600 g/mol, that the copolyester-ethercontains one or more polyether segments in an amount of about 15 toabout 35 wt.-%, in particular about 20 to about 30 wt.-%, that theamount of the copolyester-ether is selected within the range of about0.5 to about 20 wt.-%, in relation to the final composition, so that theamount of polyether segments to the total amount of base polyester andpolyester segments in the composition is about 0.7 to about 5 wt.-%, orabout 0.5 to about 1.5 wt.-%, in particular about 1 to about 2.5 wt.-%,and that the melting point, determined according to ASTM D 3418-97, ofthe copolyester-ether is about 225° C. to about 250° C., especiallyabout 235° C. to about 250° C., or in particular about 240° C. to about250° C.

Where the invention may further comprise a transition metal-basedoxidation catalyst, suitable oxidation catalysts include thosetransition metal catalysts that activate or promote the oxidation of thecopolyester-ether by ambient oxygen. Examples of suitable transitionmetals may include compounds comprising cobalt, manganese, copper,chromium, zinc, iron, or nickel. The transition metal-based oxidationcatalyst may be present in the form of a metal salt. In this case,suitable counter ions for the transition metal include, but are notlimited to, carboxylates, such as neodecanoates, octanoates, stearates,acetates, naphthalates, lactates, maleates, acetylacetonates,linoleates, oleates, palminates or 2-ethyl hexanoates, oxides,carbonates, chlorides, dioxides, hydroxides, nitrates, phosphates,sulfates, silicates or mixtures thereof. It is also possible that thetransition metal-based oxidation catalyst is incorporated in the polymermatrix during e.g. extrusion. The transition metal-based oxidationcatalyst can be added during polymerization of the polyester orcompounded into a suitable polyester thereby forming a polyester-basedmasterbatch that can be added during the preparation of the article.Advantageously, the transition metal based oxidation catalyst is acobalt compound. In the container- or preform-related embodiments of thepresent invention, it may be advantageous that the transitionmetal-based oxidation catalyst is a cobalt compound that is present inan amount of 30-200 ppm, more specifically 60-120 ppm, on basis of theweight of cobalt atom in the total composition. In themasterbatch-related embodiments of the present invention, it may beadvantageous that the transition metal-based oxidation catalyst is acobalt compound that is present in an amount of 50-5,000 ppm, morespecifically 100-2,500 ppm, on basis of the weight of cobalt in thetotal composition. In the embodiments of the present invention, it maybe advantageous that the transition metal-based oxidation catalyst issupplied as a cobalt salt, in particular a cobalt carboxylate, andespecially a cobalt C₈-C₂₀ carboxylate. The cobalt compound may bephysically separate from the copolyester-ether, for example a sheathcore or side-by-side relationship, so as not to activate thecopolyester-ether prior to melt blending into a preform or bottle.

Embodiments in some aspects of the invention may further comprise anantioxidant selected from the group consisting of hindered phenols,benzophenones, sulfur-based antioxidants, phosphites and hindered aminelight stabilizers. Examples of such antioxidants include, but are notlimited to1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene(CAS: 1709-70-2),tetrakis(2,4-di-tert-butylphenyl)-1,1-biphenyl-4,4′-diylbisphosphonite(CAS: 38613-77-3) and pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate (CAS:6683-19-8). Advantageously, one or more antioxidants are used in a totalamount of 40 ppm-10,000 ppm, more specifically 80 ppm-5,000 ppm or 120ppm-3,000 ppm, and in particular 150 ppm-2,000 ppm, on basis of thetotal weight of the one or more antioxidants to the total weight of thecomposition.

Embodiments in some aspects of the invention may further compriseadditives selected from the group consisting of dyes, pigments, fillers,branching agents, reheat agents, anti-blocking agents, anti-staticagents, biocides, blowing agents, coupling agents, flame retardants,heat stabilizers, impact modifiers, crystallization aids, lubricants,plasticizers, processing aids, buffers, and slip agents. Representativeexamples of such additives are well-known to the skilled person.

It may be advantageous that an ionic compatibilizer is present or used.Suitable ionic compatibilizers can for instance be copolyesters preparedby using ionic monomer units as disclosed in WO 2011/031929 A2, page 5,incorporated herein by reference.

One aspect of the invention refers to the use of copolyester-ether,wherein the copolyester-ether comprises one or more polyether segmentshaving a number-average molecular weight of from 200 to 5000 g/mol,wherein the one or more polyether segments are present in thecopolyester-ether in an amount of about 5 to about 45 wt.-%, and whereinthe melting point of the copolyester-ether, determined according to ASTMD 3418-97, is from 225° C. and 250° C.; for preparing a kit-of-partscomprising said copolyester-ether and physical or electronicinstructions or advise to use said copolyester-ether for preparing apreform or container. A non-limiting example of such a kit-of-parts is apackage comprising the copolyester-ether that is containing oraccompanied by a shipping document that specifies that the contents ofthe package are intended for use in preforms or containers. A furthernon-limiting example of such a kit-of-part is a package or storage formcomprising the copolyester-ether and a webpage stating that thecopolyester-ether is available for sale for use in preforms orcontainers.

In masterbatch embodiments of the present invention, it may beadvantageous that the masterbatch is mixed or packaged with anothermasterbatch comprising the transition metal based oxidation catalyst (a“salt and pepper” mixture). It may be advantageous that the othermasterbatch comprising the transition metal based oxidation catalystfurther comprises a polyester.

The disclosed compositions, masterbatches and methods may be used forpreparing articles of manufacture. Suitable articles include, but arenot limited to, film, sheet, tubing, pipes, fiber, container preforms,blow molded articles such as rigid containers, thermoformed articles,flexible bags and the like and combinations thereof. Typical rigid orsemi-rigid articles can be formed from plastic, paper or cardboardcartons or bottles such as juice, milk, soft drink, beer and soupcontainers, thermoformed trays or cups. In addition, the walls of sucharticles may comprise multiple layers of materials.

The term “comprising” encompasses “including” as well as “consisting”e.g. a composition “comprising” X may consist exclusively of X or mayinclude something additional e.g. X+Y.

The invention is further illustrated by the following examples, althoughit will be understood that these examples are included for the purposesof illustration only and are not intended to limit the scope of theinvention.

Test Procedures Number Average Molecular Weight

The number average molecular weight of the polyols is determined by thetitration method for the hydroxyl number of the polyols. Similar ASTMmethods are ASTM E222A and ASTM E222B, herein incorporated by reference.

For that 1 h of polyglycol, whereas the actual weight is dependent onthe expected hydroxyl number−(expected to be 50/hydroxyl number), wasadded into a 100 mL beaker 15 mL of dry tedrahydrofuran and the sampledissolved using a magnetic stirrer. 10 mL of p-toluenesulfonylisocyanate in 250 mL anhydrous acetonitrile was then added to thesolution. The solution was then stirred for five minutes after 1 mL ofwater was added. Then the solution was diluted to 60 mL withtetrahydrofuran and titrated with 0.1 N tetrabutyl ammonium hydroxide(TBAOH) using an automatic titrator. (TBAOH titrant: 100 mL 1MTBAOH/MeOH in 1000 mL isopropanol. Standardize against potassiumbiphthalate or benzoic acid standards. Restandardize every time theelectrode is recalibrated.)

The hydroxyl number of the polyol was calculated as followed:

${{Hydroxyl}\mspace{14mu} {number}\mspace{14mu} \left( {{OH}\#} \right)} = \frac{\left( {{V\; 2} - {V\; 1}} \right) \cdot N \cdot 56.1}{{sample}\mspace{14mu} {weight}}$

wherein

-   -   V1=Titrant volume at first equivalence point (low pH)    -   V2=Titrant volume at second equivalence point (higher oH)    -   N=Normality of TBAOH        The number molecular weight of the polyol is then calculated as        followed:

${{Molecular}\mspace{14mu} {weight}\mspace{14mu} \left( {{number}\mspace{14mu} {average}} \right)} = {\frac{112200}{{Hydroxyl}\mspace{14mu} {number}\mspace{14mu} \left( {{OH}\#} \right)}\left\lbrack \frac{g}{mol} \right\rbrack}$

Intrinsic Viscosity

The determination of the intrinsic viscosity was determined on a 0.01g/mL polymer solution in dichloroacetic acid.

Before dissolution of solid state polymerized material, the chips werepressed in a hydraulic press (pressure: 400 kN at 115° C. for about 1minute; type: PW40® Weber, Remshalden-Grunbach, Germany). 480 to 500 mgpolymer, either amorphous chips or pressed chips, were weighed on ananalytical balance (Mettler AT 400®) and dichloroacetic acid is added(via Dosimat® 665 or 776 from Metrohm) in such an amount, that a finalpolymer concentration of 0.0100 g/mL is reached.

The polymer is dissolved under agitation (magnetic stirring bar,thermostat with set point of 65° C.; Variomag Thermomodul 40ST®) at 55°C. (internal temperature) for 2.0 hrs. After complete dissolution of thepolymer, the solution is cooled down in an aluminum block for 10 to 15minutes to 20° C. (thermostat with set point of 15° C.; VariomagThermomodul 40ST®).

The viscosity measurement was performed with the micro Ubbelohodeviscometer from Schott (type 53820/II; Ø: 0.70 mm) in the Schott AVS500® apparatus. The bath temperature is held at 25.00±0.05° C. (SchottThermostat CK 101®). First the micro Ubbelohde viscometer is purged 4times with pure dichloroacetic acid then the pure dichloroacetic acid isequilibrated for 2 minutes. The flow time of the pure solvent ismeasured 3 times. The solvent is drawn off and the viscometer is purgedwith the polymer solution 4 times. Before measurement, the polymersolution is equilibrated for 2 minutes and then the flow time of thissolution is measured 3 times.

The relative viscosity (RV) is determined by dividing the flow time ofthe solution by the flow time of the pure solvent. RV is converted to IVusing the equation: IV (dl/g)=[(RV−1)×0.691]+0.063.

Determination of the Thermal Decomposition Products Detected in thePreforms

The decomposition products detected in the chips and preforms weremeasured via Headspace-GCMS. For the measurements 1 g of a powderedsample (particle size <1.0 mm) and 2 μL hexafluorisopropanol (HFIP) asthe internal standard were added in 20 g vials and then incubated for 1hour at 150° C. 1 μL of the headspace of the vials was injected in thecolumn (RTX-5, crossbond 5% diphenyl/95% dimethyl polysiloxane, 60 m,0.25 mm internal diameter) for separation. The main thermaldecomposition products were detected and analysed via mass spectrometer.

The following setup was used:

Gas Chromatograph (GC), Finnigan Focus GC (Thermo Electron Corporation)

-   -   SSL inlet        -   Mode: Split        -   Inlet T—230° C.        -   Split flow—63 mL·min⁻¹        -   Spilt ratio—70    -   Carrier        -   Constant flow    -   Ramp from 40° C. (hold for 8 min) to 300° C. (hold for 3 min)    -   T increase 15° C.·min⁻¹

Mass Spectrometer (MS), Finnigan Focus DSQ (Thermo Electron Corporation)

-   -   MS transfer line—T−250° C.    -   Ion source T—200° C.    -   Detector gain: 1.5·10⁵ (multiplier voltage 1445V)    -   Scan: 10-250 (mass range)        The following thermal decomposition products were detected in        the headspace of the powdered samples:    -   C₂-bodies—acetaldehyde    -   C₃-bodies—formic acid propyl ester, propanol, propionaldehyde    -   C₄-bodies—tetrahydrofuran

The individual values for the above C₂- to C₄-bodies were summed up togive the reported value. The standard deviation of the thermaldecomposition products is about 4% for all measurements.

Thermal Behavior

Melting temperature (T_(m)) was measured according to ASTM D 3418-97. Asample of about 10 mg was cut from various sections of the polymer chipand sealed in an aluminum pan. A scan rate of 10° C./min was used in aNetsch DSC204 instrument unit under a nitrogen atmosphere. The samplewas heated from −30° C. to 300° C., held for 5 minutes and cooled to−30° C. at a scan rate of 10° C./min prior to the second heating cycle.The melting point (T_(m)) was determined as the melting peak temperatureand was measured on the 2^(nd) heating cycle where the 2^(nd) heatingcycle is the same as the first

Haze and Color

The color of the chips and preform or bottle walls was measured with aHunter Lab ColorQuest II instrument. D65 illuminant was used with a CIE1964 10° standard observer. The results are reported using the CIELABcolor scale, L is a measure of brightness, a* is a measure of redness(+) or greenness (−) and b* is a measure of yellowness (+) or blueness(−).

The haze of the bottle walls was measured with the same instrument(Hunter Lab ColorQuest II instrument). D65 illuminant was used with aCIE 1964 10° standard observer. The haze is defined as the percent ofthe CIE Y diffuse transmittance to the CIE Y total transmission. Unlessotherwise stated the % haze is measured on the sidewall of a stretchblow molded bottle having a thickness of about 0.25 mm.

Elemental Metal Content

The elemental metal content of the ground polymer samples was measuredwith an Atom Scan 16 ICP Emission Spectrograph from Spektro. 250 mg ofthe copolyester-ether was dissolved via microwave extraction by adding2.5 mL sulfuric acid (95-97%) and 1.5 mL nitric acid (65%). The solutionwas cooled, then 1 mL hydrogen peroxide was added to complete thereaction and the solution was transferred into a 25 mL flask usingdistilled water. The supernatant liquid was analyzed. Comparison of theatomic emissions from the samples under analysis with those of solutionsof known elemental ion concentrations was used to calculate theexperimental values of elements retained in the polymer samples.

Oxygen Ingress Measurements—Non-Invasive Oxygen Determination (NIOD)

There are several methods available to determine the oxygen permeation,or transmission, into sealed packages such as bottles. In this case,non-invasive oxygen measurement systems (e.g., supplied by OxySense® andPreSens Precision Sensing) based on a fluorescence quenching method forsealed packages were employed. They consist of an optical system with anoxygen sensor spot (e.g. OxyDot®, which is a metal organic fluorescentdye immobilized in a gas permeable hydrophobic polymer) and a fiberoptic reader-pen assembly which contains both a blue LED andphoto-detector to measure the fluorescence lifetime characteristics ofthe oxygen sensor spot (e.g. OxyDot®).

The oxygen measurement technique is based upon the absorption of lightin the blue region of the metal organic fluorescent dye of the oxygensensor spot (e.g., OxyDot®), and fluorescence within the red region ofthe spectrum. The presence of oxygen quenches the fluorescent light fromthe dye as well as reducing its lifetime. These changes in thefluorescence emission intensity and lifetime are related to the oxygenpartial pressure, and thus they can be calibrated to determine thecorresponding oxygen concentration.

The oxygen level within a package such as a bottle can be measured byattaching an oxygen sensor spot (e.g., OxyDot®) inside the package. Theoxygen sensor spot is then illuminated with a pulsed blue light from theLED of the fiber optic reader-pen assembly. The incident blue light isfirst absorbed by the dot and then a red fluorescence light is emitted.The red light is detected by a photo-detector and the characteristic ofthe fluorescence lifetime is measured. Different lifetimecharacteristics indicate different levels of oxygen within the package.

Experimental Method with PET Bottle at Ambient Conditions (23° C.)

A PreSens non-invasive and non-destructive oxygen ingress measurementequipment (Fibox 3-trace meter, fiber optic cable and trace oxygensensor spots) was used to determine the oxygen permeability of thebottle at room temperature (23° C.). For a typical shelf-life test, thetrace oxygen sensor spot was first attached onto the inner side wall ofa 500 ml transparent PET bottle. The bottle was then filled withdeionized and deoxygenated water containing AgNO₃ up to a headspace ofapprox. 20 ml, inside a nitrogen circulation glove box where the oxygenlevel of the water inside the bottle was stabilized at a level wellbelow 50 ppb. These bottles were then stored in a conditioning cabinet(Binder 23° C., 50% relative humidity) and the oxygen ingresses weremonitored as a function of time using the PreSens oxygen ingressmeasurement equipment.

At a given time of measurements, an average value was first obtainedfrom about 10 readings taken on the output of the trace oxygen spot foreach bottle. This was then repeated for all the 5 bottles so as toachieve an overall averaged value for the oxygen ingress through theformulated cap and the wall of the bottle.

Oxygen measurements were made on day 0, 1, 2, 3, 8, 14, 21, 28, 42 and56. The average oxygen ingress was determined and reported as ppb asfollows:

${{Oxygen}\mspace{14mu} {{ingress}\mspace{14mu}\lbrack{ppb}\rbrack}} = \frac{\sum{{Oxygen}\mspace{14mu} {ingress}\mspace{14mu} {in}\mspace{14mu} {the}\mspace{14mu} {measurement}\mspace{14mu} {of}\mspace{14mu} {that}\mspace{14mu} {{day}\mspace{14mu}\lbrack{ppb}\rbrack}}}{\sum{{Amount}\mspace{14mu} {of}\mspace{14mu} {measurements}\mspace{14mu} {up}\mspace{14mu} {to}\mspace{14mu} {the}\mspace{14mu} {day}\mspace{14mu} {of}\mspace{14mu} {measurement}^{*}}}$ ^(*)Including  day  0

Preform and Bottle Process

Unless otherwise stated, the barrier copolyester-ether of the presentinvention was dryed for about 24 hours at 110-120° C. under nitrogenatmosphere, blended with the dry base resin (BP1) which contains thetransition metal catalyst, melted and extruded into preforms. Eachpreform for a 0.5 liter soft drink bottle, for example, employed about28 grams of the resin. The preform was then heated to about 85-120° C.and stretch-blown into a 0.5 liter contour bottle at a planar stretchratio of approx. 8. The stretch ratio is the stretch in the radialdirection times the stretch in the length (axial) direction. Thus if apreform is blown into a bottle, it may be stretched about two times inthe axial direction and stretched up to about four times in the hoopdirection giving a planar stretch ratio of up to eight (2×4). Since thebottle size is fixed, different preform sizes can be used for obtainingdifferent stretch ratios. The sidewall thickness of the bottleswas >0.25 mm.

Delamination Tests (Drop Impact Test)

Ten bottles (0.5 L) were made with from the barrier resin(copolyester-ether) and the base resin (polyester including oxidationadditive) as described above. Each bottle was filled with 500 g waterand capped securely. One at a time, each bottle was first dropped in anangle of 5° through a guide plate, then straight down from approx. 150cm onto a steel plate. The guide plate ensured that the bottlereproducibly contacted the steel plate on their sidewall. Afterwards,the bottles were inspected and visually rated for their degree ofdelamination. The delamination was ranked as excellent if nodelamination was visually detected or barely visible; as good if onlysome minor delamination detected; and as poor, if large areas ofdelamination of up to 2.5 cm were visible.

In second delamination test, twelve bottles (0.5 L) were made with fromthe barrier resin (copolyester-ether) and the base resin (polyesterincluding oxidation additive) as described above. Each bottle was filledwith 500 g water and capped securely. One at a time, each bottle wasfirst dropped in an angle of 5° through a guide plate, then straightdown from approx. 150 cm onto a steel plate. The guide plate ensuredthat the bottle reproducibly contacted the steel plate on theirsidewall. Afterwards, the bottles were inspected for delamination andcategorized as “delaminated bottle” if delamination was visuallydetected and categorized as “non-delaminated bottle” if no delaminationwas visually detected. Delamination was rated according to the totalnumber of delaminated bottles.

In a third delamination test, twelve bottles (0.5 L) were made with fromthe barrier resin (copolyester-ether) and the base resin (polyesterincluding the transition metal-based oxidation catalyst) as describedabove. Each bottle was filled with 500 g water and capped securely. Oneat a time, each bottle was first dropped in an angle of 5° through aguide plate, then straight down from approx. 150 cm onto a steel plate.The guide plate ensured that the bottle reproducibly contacted the steelplate on their sidewall. Afterwards, the bottles were inspected fortheir degree of delamination. The amount of delamination was calculatedas followed:

${{Amount}\mspace{14mu} {of}\mspace{14mu} {delamination}} = \frac{\sum{{longest}\mspace{14mu} {distance}\mspace{14mu} {across}\mspace{14mu} {the}\mspace{14mu} {delamiated}\mspace{14mu} {area}}}{\sum{{delaminated}\mspace{14mu} {bottles}}}$

EXAMPLES First Aspect Example A1. Synthesis of Copolyester-Ether (COPEE1)

Copolyester-ether was prepared using continuous polymerization process:A slurry of terephthalic (PTA) acid and glycol (EG) in a small molarexcess of glycol (PTA/EG molar ratio <1:1.15) was continuously chargedto the primary esterification reactor. The amount of slurry added to theprimary esterification reactor was controlled by a flow measuringdevice. In the primary esterification reactor terephthalic acid andglycol reacted at 250-260° C. and 2-4 bar excess pressure under waterelimination. The resulting low molecular weight esterification productwas then transferred (via pump) to another reactor (secondaryesterifier). A titanium catalyst (Sachtleben Hombifast HS06®, 12 ppm Tibased on the final polymer) and 20 weight-% of poly(tetramethyleneoxide) glycol (Terathane® Polyetherglycol, having a number averagemolecular weight of 1400 g/mole, stabilized with 200 ppm Ethanox® 330)based on the final polymer weight were then added to the reactionmixture and the polycondensation, the elimination of glycol underreduced pressure, started at 250-260° C. The dwell time of the reactionmixture (pre-condensate) was again controlled by a flow measuringdevice. The pre-condensate was then discharged consecutively in twodownstream reactors where the dwell time was controlled via the level ofthe reaction mixture in each reactor. In both reaction vessels glycolwas distilled out of the reaction mixture under increased temperatureand reduced pressure until the desired polymerization degree wasachieved. The desired polymer melt flowed through the reactor dischargepump in a cooling bath with deionized water. After the polymer strandcooled, it was pelletized with Pell-tec pelletizer.

The intrinsic viscosity of the final copolyester-ether polymercompositions was 0.693 dl/g.

Example A2. Synthesis of the Base Polyester (BP1)

The base resin was prepared using continuous process: A slurry ofterephthalic acid, isophthalic acid (3.05 wt.-% based on the finalpolymer) and glycol in a small molar excess of glycol (PTA/EG molarratio <1:1.08) was continuously charged to the primary esterificationreactor. The amount of slurry added to the primary esterificationreactor was controlled by a flow measuring device. In the primaryesterification reactor terephthalic acid and glycol react at 250-260° C.and 2-4 bar excess pressure under water release. The resulting lowmolecular weight esterification product was then transferred (via pump)to another reactor (secondary esterifier). A titanium catalyst(Sachtleben Hombifast HS06®, 7 ppm Ti based on the final polymer) wasthen added to the reaction mixture and the polycondensation, theelimination of glycol under reduced pressure, started at 260-280° C. Thedwell time of the reaction mixture (pre-condensate) is again controlledby a flow measuring device. The pre-condensate was then dischargedconsecutively in two downstream reactors whereas the dwell time wascontrolled via level of the reaction mixture in each reactor. In bothreaction vessels further glycol was distilled out of the reactionmixture under increased temperature and reduced pressure until thedesired polymerization degree is achieved. The oxidation catalyst (75ppm Cobalt as Cobalt-stearate, CAS: 1002-88-6) was added late as a meltto the reaction mixture shortly before the polymer melt flowed throughthe reactor discharge pump in a cooling bath with deionized water. Afterthe polymer strand cooled, it was pelletized with Pell-tec pelletizer.

The resulting polymer chips were crystallized for approx. 4 hours at160° C., solid stated under vacuum at a temperature of 230° C. forapprox. 7 hours to the desired intrinsic viscosity value (˜IV-value:0.860 dl/g) and then cooled to ambient temperature.

Example A3. Compounding of Copolyester-Ether (COPE E1) with DifferentStabilizers

The copolyester-ether COPE E1 described in Example A1 with an intrinsicviscosity of 0.693 dl/g was used for the compounding trials. Prior tothe extrusion the COPE E1 was dried at 160° C. under vacuum for 5 hoursto remove residual moisture. The COPE E1 was then mixed with differentpowdered additives via salt and pepper method and the resulting mixtureswere subsequently extruded using an intermeshing, co-rotating, twinscrew extruder manufactured by Leistritz AG. The process conditions usedduring the experiment are described below:

-   -   Extruder type: (Leistritz Micro 27 36D), co-rotating, extruder        screw diameter 27 mm, screw length to diameter ratio (L:D) ratio        is 36:1    -   Operation conditions: T0 cooling water temperature/T1 210° C./T2        215° C./T3 210/T4-T5 240° C./T6-T8 210° C./T9 209° C.    -   No vacuum level in degassing area    -   Polymer flow rate 8 kg/h    -   Type of granules: cylindrical, length 3 mm and diameter 2 mm

The molten materials were extruded into a water bath and thenpelletized. The intrinsic viscosity of the compounded material is about0.668 dl/g. The kind and amount of the additives and the thermaldecomposition products are summarized in the Tables A1 and A2 below.Table A1 shows the Hindered Amine Light Stabilizers (HALS) of theinvention and Table A2 shows comparative stabilizers (UV-absorbers andthermo-oxidative stabilizers):

TABLE A1 Sample 1 2 3 4 5 6 7 8 9 10 11 12 13 HALS¹ — Uvinul ® 4050Uvinul ® 5050 Uvinul ® 5062 Total — 156 313 625 1250 2500 1513 3025 6050781 1563 2500 3125 amount [ppm] Active — 10 20 39 78 156 39 78 156 39 77123 154 N² [ppm] Thermal C₂-C₄ decomposition products (ppm, detected inthe resin) C₂-C₄ 2436 1719 86 98 131 111 57 91 84 1918 579 1249 76decomp. ¹Uvinul 4050(N,N′-bisformyl-N,N′-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylendiamine),CAS: 124172-53-8 Uvinul ® 5050 (sterically hindered amine, oligomeric),CAS: 152261-33-1 Uvinul ® 5062 (sterically hindered amine, oligomeric),CAS: 65447-77-0 ²Active N: Amount of nitrogen contained in functionalgroups which have the ability to generate a stable nitroxyl radical

TABLE A2 Sample 14 15 16 17 18 19 20 21 23 UV-absorber¹ Thermo-oxidativestabilizer² Additive Hostavin ® Tinuvin ® Tinuvin ® Uvinul ® Hostanox ®Aro8 234 1577 3030 PEP-Q Ethanox ® 330 [ppm] 2500 2500 2500 2500  200 625 625 1250 2500 Thermal decomposition products (ppm, detected in theresin) C₂-C₄ 1971 1884 2314 2098 2288 1996  54  52  46 decomp.¹Hostavin ® Aro8 (2-Hydroxy-4-n-octyloxybenzophenone), CAS: 1843-05-6Tinuvin ® 234(2-(2F-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, CAS:70321-86-7 Tinuvin ® 1577(2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, CAS:147315-50-2 Uvinul ® 3030 (2-Propenoic acid,2-cyano-3,3-diphenyl-,2,2-bis[[(2-cyano-1-oxo-3,3-diphenyl-2-propenyl)oxy]methyl]-1,3-propanediyl ester), CAS: 178671-58-4 ²Hostanox ®PEP-Q(Diphosphonite antioxidant), CAS: 119345-01-6 Ethanox ® 330(1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, CAS:1709-70-2

As is evident from the above Table A1, the HALS compounds of theinvention are substantially reducing the amount of C₂-C₄ decompositionproducts. Different HALS stabilizers of the invention are of similarpotency with the exception of Uvinul® 5062 which is slightly lesspotent. Without being bound by theory, it may be speculated that thisHALS stabilizer has first to be cleaved in-situ to yield a stericallyhindered amine radical that is capable of scavenging radicals.Nevertheless, Uvinul® 5062 is more efficient in reducing C₂-C₄decomposition products than other types of stabilizers such as Hostavin®Aro8, Tinuvin® 234, Tinuvin® 1577, Uvinul® 3030 and Hostanox® PEP-Q(Table 2).

Example A4. Influence of Different Stabilizers on Thermal DecompositionProducts and Oxygen Barrier in Preforms and Bottles

Unless otherwise stated, various modified barrier copolyester-ether ofthe present invention (see above Table A1 and A2) were dryed for about24 hours at 110-120° C. under nitrogen atmosphere, blended with the drybase resin (BP1 from Example A2) which contains the transition metalcatalyst, injection-molded into preforms and further stretch-blow moldedinto bottles (see below Table A3). The ratio of barrier resin to baseresin was chosen as 5.0/95.0 (wt. by wt.). The preforms were stretchblow molded into 500 mL, 28 g bottles. The oxygen permeation, the colorvalues as well as the haze of these bottles were measured. The bottleswere then either cut and powdered (<0.1 mm) to determine the thermalby-product level or barrier measurement (as described in the TestProcedures). For reasons of better grindability, the thermaldecomposition products were detected in the ground preforms and thebarrier performance was measured in the bottles.

TABLE A3 Sample I II III IV V Stabilizer — Uvinul ® Hostavin ®Hostanox ® Ethanox ® 4050 Aro8 PEP-Q 330 Amount stabilizer — 2500 25002500 625 (added to the Copolyester-ester resin) [ppm] Thermaldecomposition products 461 234 416 387 432 (detected in the preforms)Total C₂-C₄ [ppm] Barrier performance after 56 days 11 23 32 95 226(measured in the bottles) [ppb]

From the above Table A3, it is evident that HALS compounds of formula(I) are capable of substantially reducing the amount of C₂-C₄decomposition products in final products such as preforms and bottles.At the same time, oxygen barrier properties of bottles are minimallyaffected. In comparison, other stabilizers do not provide the sameperformance: Hostavin® Aro8 does not yield a comparable reduction indegradation products and is also more negatively impacting barrierperformance. Hostanox® PEP-Q is inferior in preventing degradation andprovides substantially deteriorated barrier performance. Finally,Ethanox® 330 leads to poor oxygen barrier properties already at 625 ppmaddition level. At the same concentration, Ethanox® 330 also providespoor protection against degradation.

Example A5. Influence of the Amount of HALS

In the next test series, the concentration of a HALS according to theinvention was successively reduced. The following samples summarized inTable A4 were prepared as described in Example A4:

TABLE A4 Sample I II VI VII VIII Stabilizer — Uvinul ® 4050 Amountstabilizer — 2500 1250 625 313 (added to the Copolyester-ester resin)[ppm] Thermal decomposition products 461 234 224 300 308 (detected inthe preforms) Total C₂-C₄ [ppm] Barrier performance after 56 days 11 2326 27 12 (measured in the bottles) [ppb]

As is evident from the above Table A4, the HALS compounds of theinvention retain their performance at very low concentrations.

Example A6. Terephthalic Acid (PTA)—Process for Preparing FurtherCopolyester-Ethers

Terephthalic acid (PTA) and ethylene glycol (EG) in a small molar excessof glycol (PTA/EG molar ratio <1:1.15) were charged under nitrogen intoa reactor equipped with a condenser, reflux column and stirrer. Thematerials were then stirred continuously, heated up to a temperature of230° C. meanwhile undergo an esterification to form a low molecularweight esterification product under water release. Then,poly(tetramethylene oxide) glycol (Terathane® Polyetherglycol) ofdifferent molecular weights and different wt.-% ratiospoly(tetramethylene oxide) glycol to PTA/EG), based on the finalpolymer, and Ethanox® 330 (CAS: 1709-70-2, 200 ppm, based on the weightof Terathane® Polyetherglycol) were then added together with a titaniumcatalyst (Sachtleben Hombifast HS06®, 25 ppm Ti, based on the polymer)to the reaction mixture. The mixture was transferred to an autoclave. Ina time range of 30 minutes the pressure was reduced to <0.3 mm Hg whilethe temperature was ramped to 250° C. The reaction mixture was held atthis temperature for approx. 130 min. Ten minutes before the product wasextruded into chilled water the reactor was charged with nitrogen anddifferent amounts of stabilizers were added in the reactor to thepolymer melt. The mixture was stirred for additional 10 minutes. Afterthe polymer strand cooled, it was pelletized with a Scheer-baypelletizer.

The compositions of the prepared copolyester-ethers are listed in thebelow Tables A5 and A6.

TABLE A5 Terathane ® Polyether- glycol/ Amount Active Terathane ® PTA-EGstabilizer N₂ Resin (g/mol) [wt. by wt.] Stabilizer (ppm) [ppm] 24 140035/65 Uvinul ® 4050 375 47 25 1400 35/65 Uvinul ® 4050 750 93 26 140035/65 Uvinul ® 4050 15000 1866 27 1400 70/30 Uvinul ® 4050 375 47 281400 70/30 Uvinul ® 4050 750 93 29 1400 70/30 Uvinul ® 4050 1500 187 301400 70/30 Uvinul ® 4050 15000 1866 31 650 35/65 Uvinul ® 4050 375 47 32650 35/65 Uvinul ® 4050 1500 187 33 2000 35/65 Uvinul ® 4050 375 47 342000 35/65 Uvinul ® 4050 1500 187

TABLE A6 Terathane ® Polyether- glycol/ Amount Active Terathane ® PTA-EGstabilizer N₂ Resin (g/mol) [wt. by wt.] Stabilizer (ppm) [ppm] 35 140035/65 Uvinul ® 5050 908 47 36 1400 35/65 Uvinul ® 5050 3630 187 37 140035/65 Tinuvin ® 622 469 23 38 1400 35/65 Tinuvin ® 622 1875 92

Example A7. Preparation of Preforms and Bottles

The above barrier copolyester-ether of the present invention (see aboveTables A5 and A6) were dryed for about 24 hours at 110-120° C. undernitrogen atmosphere, blended with the dry base resin (either resin2300K, available from INVISTA, or BP1, from Example A2) in the amountsindicated below and injection-molded into preforms which were furtherstretch-blow molded into 500 mL, 28 g bottles. The oxygen permeation ofthese bottles was measured. For reasons of better grindability, thethermal decomposition products were detected in the ground preforms.

Example A8. Variation Experiments

In a first series, preforms and bottles using Sb-based resin 2300 K,Terathane® 1400, a COPE-ratio of 35/65 (polyetherglycol/PTA-EG [wt. bywt.]) and the HALS Uvinol® 4050 were prepared:

TABLE A7 Weight Terathane C2-C4 Stabilizer Ratio in final (pre- Barrierin COPE PET/ composition forms) performance Run [ppm] COPE [wt-%] [ppm][28 days, ppb] 140557 1500 99.0/1.0 0.35 57 383 140173 750 97.5/2.50.875 383 156 140171 375 95.0/5.0 1.75 852 110

As is evident from the above Table A7, like in the Ti-based resins, theconcentration of a HALS can be significantly reduced while stillproviding good protection against degradation. The barrier performanceis still acceptable for an Sb-based resin system.

Next, preforms and bottles using Sb-based resin 2300 K, Terathane® 1400,a COPE-ratio of 35/65 (polyetherglycol/PTA-EG [wt. by wt.]) and the HALSUvinol® 4050 were prepared. However, this time, the amount of Terathanein the final composition was substantially increased:

TABLE A8 Weight Terathane C2-C4 Stabilizer Ratio in final (pre- Barrierin COPE PET/ composition forms) performance PTP [ppm] COPE [wt.-%] [ppm][28 days, ppb] 140175 750 80.0/20.0 7 513 192 140178 15000 80.0/20.0 71039 426

As is evident from the above table, HALS also significantly reducedC2-C4 decomposition products at very high terathane concentrations of 7wt.-% in the final blend. Since Terathane is the source of the C2-C4decomposition products, the above results represent a very goodperformance for HALS. The barrier performance is still acceptable for anSb-based resin system.

In another test series, it was investigated whether HALS is able toreduce decomposition products for other molecular weights than Terathane1400. Preforms and bottles using Sb-based resin 2300 K, Terathane® 650,and 2000, a COPE-ratio of 35/65 (polyetherglycol/PTA-EG [wt. by wt.])and the HALS Uvinol® 4050 were prepared:

TABLE A9 Tera- thane Barrier Stabi- Weight in final C2-C4 perfor- lizerin Ratio compo- (pre- mance Tera- COPE PET/ sition forms) [28 days, PTPthane [ppm] COPE [wt.-%] [ppm] ppb] 140525 T2000 375 90.0/10.0 3.5 1169123 140520 T650 375 90.0/10.0 3.5 904 317

As is evident from the above table, HALS is equally able to reduce theC2-C4 decomposition products from polyethers of different weight. At alow molecular weight of 650 g/mol, the polyether is having diminishedbut still acceptable oxygen barrier properties. At a high molecularweight of 2000 g/mol, the polyether has still excellent oxygen barrierproperties for an Sb-based system.

In the next test series, the ratio of polyester and polyether in thecopolyester-ether was reversed. Preforms and bottles using Sb-basedresin 2300 K, Terathane® 1400, a COPE-ratio of 70/30, instead of 35/65,(polyetherglycol/PTA-EG [wt. by wt.]) and the HALS Uvinol® 4050 wereprepared:

TABLE A10 Weight Terathane C2-C4 Stabilizer Ratio in final (pre- Barrierin COPE PET/ composition forms) performance PTP [ppm] COPE [wt.-%] [ppm][28 days, ppb] 140317 15000  90.0/10.0 7 938 279 140316 1500  80.0/20.014 1315 370 140314 1500 99.0/1.0 0.7 280 104 140315 1500 95.0/5.0 3.5951 104 140311 750 97.5/2.5 1.75 508 100 140312 750  90.0/10.0 7 1102149 140310 375 95.0/5.0 3.5 880 91

As is evident from the above table, independently from the ratio ofpolyether to polyester in the copolyester-ether, HALS is capable ofreducing C2-C4 decomposition products while maintaining good barrierproperties. Even at extremely high loadings of 15,000 ppm, HALS isproviding satisfactory barrier properties and low decomposition products(given the high concentration of polyether at 7 wt.-%). In addition, theabove table shows that even at very high polyether concentrations of 14wt.-%, HALS is providing good barrier properties and low decompositionproducts (given the high concentration of polyether at 14 wt.-%).

In another test trial, the structure of the HALS was varied. Preformsand bottles using Ti-based resin BP1, Terathane® 1400, a COPE-ratio of35/65, (polyetherglycol/PTA-EG [wt. by wt.]) and the HALS Uvinol® 4050and 5050 as well as Uvinul® 5062 were prepared:

TABLE A11 Tera- thane Barrier Stabi- Weight in final C2-C4 perfor- lizerin Ratio compo- (pre- mance COPE PET/ sition forms) [28 days, PTP HALS[ppm] COPE [wt.-%] [ppm] ppb] 140179 U4050 375 95.0/5.0 1.75 857 21140304 U5050 908 95.0/5.0 1.75 729 24 140305 U5050 3630 95.0/5.0 1.75751 26 140306 U5062 469 95.0/5.0 1.75 734 21 140307 U5062 1875 95.0/5.01.75 642 22

As is evident from the above table, various HALS derivatives at variousconcentrations were equally able in providing excellent barrierproperties and low decomposition products (given the high loading withpolyether).

Second Aspect Example B1. General Synthesis of the Base Polyesters

The base resins were either received from Invista Resin&Fibers GmbH orprepared using continuous process: A slurry of terephthalic acid (PTA),isophthalic acid (3.05 wt.-% based on the final polymer) and glycol in asmall molar excess of glycol (EG) (PTA/EG molar ratio <1:1.08) werecontinuously charged to the primary esterification reactor. The amountof slurry added to the primary esterification reactor was controlled bya flow measuring device. In the primary esterification reactor,terephthalic acid and glycol react at 250-260° C. and 2-4 bar excesspressure under water release. The resulting low molecular weightesterification product was then transferred (via pump) to anotherreactor (secondary esterifier). A catalyst-glycol solution was thenadded to the reaction mixture and the polycondensation, the eliminationof glycol under reduced pressure started at 260-280° C. The dwell timeof the reaction mixture (pre-condensate) was again controlled by a flowmeasuring device. The pre-condensate was then discharged consecutivelyin two downstream reactors whereas the dwell time was controlled vialevel of the reaction mixture in each reactor. In both reaction vesselsfurther glycol was distilled out of the reaction mixture under increasedtemperature and reduced pressure until the desired polymerization degreeis achieved. Dependent on the desired base resins differentconcentration of the oxidation catalyst Co-Stearate (CAS: 1002-88-6)(see Table B1 below) were added late as a melt to the reaction mixtureshortly before the polymer melt flowed through the reactor dischargepump in a cooling bath with deionized water. After the polymer strandcooled, it was pelletized with a Pell-tec pelletizer.

The resulting polymer chips were crystallized for approx. 4 hours at160° C., solid stated under vacuum at a temperature of 230° C. forapprox. 7 hours to the desired intrinsic viscosity value (˜IV-value:0.860 dl/g) and then cooled to ambient temperature.

An overview of the synthesized resin compositions as well as theintrinsic viscosities of the solid stated resins is set forth in TableB1.

TABLE B1 Catalyst added [ppm] Cobalt Intrinsic viscosity Resin Ti² Sb³[ppm] (IV, SSP) [dl/g] Sb-BaseR1¹ — 250 — 0.81 Sb-BaseR2 — 250 75 0.934Ti-BaseR1 7 — — 0.86 Ti-BaseR2 45 0.742 Ti-BaseR3 75 0.797 ¹Commercial1101 resin, received from Invista Resin&Fibers GmbH ²Sachtleben ®Hombifast HS06 ³Sb₂O₃

Example B2. Synthesis of Copolyester-Ether—COPE (CP) Barrier Resins(BarrierR1-4)

Copolyester-ether was prepared using continuous polymerization process:A slurry of terephthalic acid and glycol in a small molar excess ofglycol (PTA/EG molar ratio <1:1.15) were continuously charged to theprimary esterification reactor. The amount of slurry added to theprimary esterification reactor was controlled by a flow measuringdevice. In the primary esterification reactor, terephthalic acid andglycol reacted at 250-260° C. and 2-4 bar excess pressure under waterelimination. The resulting low molecular weight esterification productwas then transferred (via pump) to another reactor (secondaryesterifier). A titanium catalyst (Sachtleben Hombifast HS06®, 12 ppm Tibased on the final polymer) and different amounts of poly(tetramethyleneoxide) glycol (Terathane® Polyetherglycol, having a number averagemolecular weight of 1400 g/mole, stabilized with 200 ppm Ethanox® 330,CAS: 1709-70-2) based on the final polymer weight were then added to thereaction mixture. The amounts of Terathane® Polyetherglycol added areindicated in Table B2 below. The polycondensation, the elimination ofglycol under reduced pressure started at 250-260° C. The dwell time ofthe reaction mixture (pre-condensate) was again controlled by a flowmeasuring device. The pre-condensate was then discharged consecutivelyin two downstream reactors where the dwell time was controlled via thelevel of the reaction mixture in each reactor. In both reaction vesselsglycol was distilled out of the reaction mixture under increasedtemperature and reduced pressure until the desired polymerization degreewas achieved. The desired polymer melt flowed through the reactordischarge pump into a cooling bath filled with deionized water. Afterthe polymer strand cooled, it was pelletized with a Pell-tec pelletizer.

The compositions of the final copolyester-ethers as well as intrinsicviscosities of the resins are shown in Table B2 below.

TABLE B2 Terathane ® Polyetherglycol/ Intrinsic viscosity Sample PTA-EG¹[wt. by wt.] (IV) [dl/g] BarrierR1 10/90 0.739 BarrierR2 20/80 0.657BarrierR3 25/75 0.701 BarrierR4 30/70 0.718 ¹PTA/EG molar ratio <1:1.15

Example B3. Synthesis of Stabilized Copolyester-Ether—COPE Barrier Resin(BarrierR5)

Synthesis of the Terathane® Polyetherglycol (M_(N)—1400 g/mol)/PTA-EGcopolymer with a certain additive package via late addition:Terephthalic acid, ethylene glycol (molar ratio PTA/EG molar ratio<1:1.15), 43 wt.-% of poly(tetramethylene oxide) glycol (Terathane®Polyetherglycol, having a number average molecular weight of 1400g/mole, stabilized with 200 ppm Ethanox® 330) based on the final polymerweight and a catalyst solution (Sachtleben® Hombifast HS06, 17 ppm Titanbased on the final polymer) were polymerized under continuouspolymerization process conditions as described above (see Example B2).2500 ppmN,N′-bisformyl-N,N′-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-hexa-methylendiamine(Uvinul®4050, CAS: 124172-53-8), 2500 ppm2-Hydroxy-4-n-octyloxybenzophenone (Hostavin® Aro8, CAS: 1843-05-6) and200 ppmTetrakis(2,4-di-tert-butylphenyl)-1,1-biphenyl-4,4′-diylbisphosphonite(Hostanox® PEP-Q, CAS: 38613-77-3) were added late as a melt to thereaction mixture shortly before the polymer melt flowed through thereactor discharge pump in a cooling bath with deionized water. After thepolymer strand cooled, it was pelletized with a Pell-tec pelletizer. Theintrinsic viscosity of the final stabilized copolyester-ether barrierresin R5 was 0.855 dl/g.

Example B4. Preform and Bottle Properties Oxygen Barrier Properties ofBarrier Resin and Base Resins Excluding an Oxidation Catalyst

In the following example, the oxygen barrier properties of base resinsprepared by using titanium-based and antimony-based polycondensationcatalysts were verified for comparative purposes.

Base resins without an oxidation catalyst as indicated in the Table B1were blended with the commercial Oxyclear® 3500 barrier resin, receivedfrom Invista Resins&Fibers GmbH, and injection molded into preforms. Thepreforms were stretch blow molded into 500 mL, 28 g bottles. The oxygenpermeation was measured. The compositions of the bottles as well asaverage oxygen ingress over 56 days are depicted in Table B3.

TABLE B3 Oxygen Ratio Barrier ingress Sam- resin/Base Base Resin (ppb,ple resin [wt.-%] Barrier resin composition composition 56 days) 12.0/98.0 commercial Oxyclear ® Ti-BaseR1 742 2 3500 barrier resinSb-BaseR1 818

As is evident from the above Table B3, the base resins containing theantimony-based polycondensation catalyst exhibit no noticeable activeoxygen scavenging activity (818 ppb after 56 days). The titanium-basedpolycondensation catalyst also provides very poor to negligible oxygenbarrier properties (742 ppb after 56 days).

Oxygen Barrier Properties of Barrier Resins and Base Resins Including anOxidation Catalyst

Different dried and solid stated base resins as indicated in the TableB1 were blended with the stabilized barrier resin R5 (see Example B3),described above, and injection molded into preforms. The preforms werestretch blow molded into 500 mL, 28 g bottles. The oxygen permeation wasmeasured. The compositions of the bottles as well as average oxygeningress over 56 days are depicted in Table B4.

TABLE B4 Ratio Barrier Resin composition Barrier Terathane ® Base ResinOxygen Wt.-% resin/Base Polyether- Name ingress Ratio resinglycol/PTA-EG (amount Co (ppb, 56 transition Run [wt.-%] Name [wt. bywt.] in resin) days) metal:Ti 3 2.3/97.7 BarrierR5 43/57 Sb-BaseR2 310192:1  (75 ppm Co) 4 Ti-BaseR3 51 10:1 (75 ppm Co) 5 2.0/98  Oxyclear  ®50/50 Sb-BaseR2 141 1101:1  3500 (75 ppm Co) 6 barrier Ti-BaseR3 32 10:1resin (75 ppm Co)

As is evident from the above Table B4, the use of a titanium compound incombination with a transition metal based oxidation catalystsubstantially reduces the oxygen ingress in the bottle (51 and 32 ppbafter 56 days, respectively). In addition, the oxygen barrier issubstantially improved in comparison to the antimony-based resins (51vs. 310 ppb and 32 vs. 141 ppb, respectively). The improvement issubstantially higher than would be expected in light of the very poor tonegligible oxygen barrier properties provided by the titaniumpolycondensation catalyst on its own (see above Oxygen barrierproperties of barrier resin and base resins excluding an oxidationcatalyst).

Oxygen Barrier Properties of Barrier Resins Differing in theirCompositions

Ti-BaseR3 as indicated in the Table B1 was blended with differentbarrier resins as indicated in Table B2 and injection molded intopreforms. The preforms were stretch blow molded into 500 mL, 28 gbottles, and the oxygen permeation was measured. The compositions of thebottles as well as average oxygen ingress over 56 days are depicted inTable B5.

TABLE B5 Barrier Resin composition Barrier Terathane ® Base Resin OxygenWt.-% resin/Base Polyether- composition ingress Ratio resinglycol/PTA-EG Co (ppb, 56 transition Run [wt.-%] Name [wt. by wt.] Name[ppm] days) metal:Ti 7 10.0/90.0  BarrierR1 10-90 Ti-BaseR3 75 21 10:1 85.0/95.0 BarrierR2 20-80 23 10:1 9 4.0/96.0 BarrierR3 25-75 30 10:1 103.3/96.7 BarrierR4 30-70 41 11:1

As is evident from the above Table B5, the variation of the Terathane®Polyetherglycol/PTA-EG ratio further improves the oxygen barrierproperties in the presence of a titanium compound. There is a trend thatchanging the Terathane® Polyetherglycol/PTA-EG ratio from e.g. 50:50 to10:90 improves oxygen barrier.

Oxygen Barrier Properties of Barrier Resin and Base Resins Including anOxidation Catalyst that Differ in its Concentration

Different dried and solid stated base resins as indicated in the TableB1 were blended with the barrier resin BarrierR5 (see Example B3) andinjection molded into preforms. The preforms were stretch blow moldedinto 500 mL, 28 g bottles. The oxygen permeation was measured. Thecompositions of the bottles as well as average oxygen ingress over 56days are depicted in Table B6.

TABLE B6 Barrier Resin composition Barrier Terathane ® Base Resin OxygenWt.-% resin/Base Polyether- composition ingress Ratio resinglycol/PTA-EG Co (ppb, 56 transition Run [wt.-%] Name [wt. by wt.] Name[ppm] days) metal:Ti 11 2.3/97.7 BarrierR5 43/57 Ti-BaseR2 45 39 4:1 4Ti-BaseR3 75 51 6:1

As is evident from the above Table B6, the presence of a titaniumcompound in the bottle resin composition allows reducing the amount ofcobalt oxidation catalyst required for obtaining satisfying oxygenbarrier properties.

Third Aspect Example C1. Synthesis of the Base Polyester

The base resins were either received from Invista Resin&Fibers GmbH orprepared using continuous process: A slurry of terephthalic acid (PTA),isophthalic acid (3.05 wt.-% based on the final polymer) and glycol (EG)in a small molar excess of glycol (PTA/EG molar ratio <1:1.08) werecontinuously charged to the primary esterification reactor. The amountof slurry added to the primary esterification reactor was controlled bya flow measuring device. In the primary esterification reactor,terephthalic acid and glycol react at 250-260° C. and 2-4 bar excesspressure under water release. The resulting low molecular weightesterification product was then transferred (via pump) to anotherreactor (secondary esterifier). A catalyst-glycol solution was thenadded to the reaction mixture and the polycondensation, the eliminationof glycol under reduced pressure started at 260-280° C. The dwell timeof the reaction mixture (pre-condensate) was again controlled by a flowmeasuring device. The pre-condensate was then discharged consecutivelyin two downstream reactors whereas the dwell time was controlled vialevel of the reaction mixture in each reactor. In both reaction vesselsfurther glycol was distilled out of the reaction mixture under increasedtemperature and reduced pressure until the desired polymerization degreeis achieved. The oxidation catalyst (75 ppm cobalt as Cobalt-stearate,CAS: 1002-88-6) was added late as a melt to the reaction mixture shortlybefore the polymer melt flowed through the reactor discharge pump in acooling bath with deionized water. After the polymer strand cooled, itwas pelletized with a Pell-tec pelletizer.

The resulting polymer chips were crystallized for approx. 4 hours at160° C., solid stated under vacuum at a temperature of 230° C. forapprox. 7 hours to the desired intrinsic viscosity value (˜IV-value:0.860 dl/g) and then cooled to ambient temperature.

An overview of the synthesized resin compositions as well as theintrinsic viscosities of the solid stated resins is set forth in TableC1.

TABLE C1 Catalyst added [ppm] Cobalt Intrinsic viscosity Resin Ti² Sb³[ppm] (IV, SSP) [dl/g] Sb-BaseR1¹ — 250 75 0.86 Sb-BaseR2 — 250 75 0.934Ti-BaseR1 7 — 75 0.797 ¹2300K resin, received from Invista Resin&FibersGmbH ²Sachtleben ® Hombifast HS06 ³Sb₂O₃

Example C2—General Synthesis of the Barrier Resins

Copolyester-ether was prepared using continuous polymerization process:A slurry of terephthalic acid and glycol in a small molar excess ofglycol (PTA/EG molar ratio <1:1.15) were continuously charged to theprimary esterification reactor. The amount of slurry added to theprimary esterification reactor was controlled by a flow measuringdevice. In the primary esterification reactor, terephthalic acid andglycol reacted at 250-260° C. and 2-4 bar excess pressure under waterelimination. The resulting low molecular weight esterification productwas then transferred (via pump) to another reactor (secondaryesterifier). A titanium catalyst (Sachtleben Hombifast HS06®, 12 ppm Tibased on the final polymer) and different amounts of poly(tetramethyleneoxide) glycol (Terathane® Polyetherglycol, having a number averagemolecular weight of 1400 g/mole, stabilized with 200 ppm Ethanox® 330,CAS: 1709-70-2) based on the final polymer weight were then added to thereaction mixture. The amounts of Terathane® Polyetherglycol added areindicated in below Table C2. The polycondensation, the elimination ofglycol under reduced pressure started at 250-260° C. The dwell time ofthe reaction mixture (pre-condensate) was again controlled by a flowmeasuring device. The pre-condensate was then discharged consecutivelyin two downstream reactors where the dwell time was controlled via thelevel of the reaction mixture in each reactor. In both reaction vesselsglycol was distilled out of the reaction mixture under increasedtemperature and reduced pressure until the desired polymerization degreewas achieved. The desired polymer melt flowed through the reactordischarge pump into a cooling bath filled with deionized water. Afterthe polymer strand cooled, it was pelletized with a Pell-tec pelletizer.

The compositions of the final copolyester-ethers as well as theintrinsic viscosities of the resins are shown in Table C2 below.

TABLE C2 Terathane ® Polyetherglycol/ Intrinsic viscosity Sample PTA-EG¹[wt. by wt.] (IV) [dl/g] BarrierR1 10/90 0.739 BarrierR2 20/80 0.657BarrierR3 30/70 0.718 ¹PTA/EG molar ratio <1:1.15

Example C3—Preform and Bottle Properties

Ti-BaseR3 as indicated in the Table C1 was blended with differentbarrier resins as indicated in Table C2 and injection molded intopreforms. The preforms were stretch blow molded into 500 mL, 28 gbottles, and the oxygen permeation was measured. The compositions of thebottles as well as average oxygen ingress over 56 days are depicted inTable C3.

TABLE C3 Barrier Resin composition Ratio Barrier Terathane ® Base ResinOxygen Wt.-% resin/Base Polyether- composition ingress Ratio resinglycol/PTA-EG Co (ppb, 56 transition Run [wt.-%] Name [wt. by wt.] Name[ppm] days) metal:Ti 5 10.0/90.0  BarrierR1 10-90 Ti-BaseR1 75 21 10:1 65.0/95.0 BarrierR2 20-80 23 10:1 7 3.3/96.7 BarrierR3 30-70 41 10:1

As is evident from the above Table C3 and also FIG. 1, the variation ofTerathane® Polyetherglycol/PTA-EG ratio from 30/70 to 10/90 reduces thespike in oxygen ingress seen in the first days after compounding in alinear fashion in the tested titanium-containing blends.

Fourth Aspect Synthesis of Copolyester-Ethers, Batch Process

Examples D1 and D2 illustrate batch processes for the preparation ofcopolyester-ethers. The proportions of the various components used inthis example can be varied as required, as understood by the personskilled in the art.

Example D1. Terephthalic Acid (PTA)—Process (Samples 1-6)

Terephthalic acid (PTA) and ethylene glycol (EG) in a small molar excessof glycol (PTA/EG molar ratio <1:1.15) were charged under nitrogen intoa reactor equipped with a condenser, reflux column and stirrer. Thematerials were then stirred continuously, heated up to a temperature of230° C. meanwhile undergo an esterification to form a low molecularweight esterification product under water release. Then,poly(tetramethylene oxide) glycol (Terathane® Polyetherglycol) ofdifferent molecular weights as indicated in the below Table D1, in anequivalent amount to 50 wt.-% of the final polymer, and Ethanox® 330(CAS: 1709-70-2, 200 ppm based on the weight of Terathane®Polyetherglycol,) were then added together with a titanium catalyst(Sachtleben Hombifast HS06®, 20 ppm Ti based on the polymer) to thereaction mixture. The mixture was transferred to an autoclave. In a timerange of 30 minutes the pressure was reduced to <0.3 mm Hg while thetemperature was ramped to 250° C. The reaction mixture was held at thistemperature for approx. 130 min, then the reactor was pressurizedslightly with nitrogen, and the product was extruded into chilled water.After the polymer strand cooled, it was pelletized with a Scheer-baypelletizer.

The compositions of the final copolyester-ethers as well as the thermalbehavior are shown in Table D1 below.

TABLE D1 Sample 1 2 3 4 5 6 Terathane ® Polyetherglycol 250 650 10001400 2000 2900 [g/mol] T_(m) [° C.] — 176 205 224 244 246

Example D2. Dimethyl Terephthalate (DMT)—Process (Samples 7-12)

Dimethyl terephthalate, a molar excess of ethylene glycol (1:2.1 mole)and zinc acetate (50 ppm Zn) as the ester interchange catalyst werecharged under nitrogen into a reactor equipped with a condenser, refluxcolumn and stirrer. The materials were stirred continuously during thetransesterification and were heated to a temperature of 160-230° C.under atmospheric pressure until the ester interchange reaction wascomplete, as evidenced by the amount of methanol removed. Triethylphosphonoacetate (33 ppm P, CAS: 867-13-0), poly(tetramethylene oxide)glycol (Terathane Polyetherglycol) of different molecular weights asindicated in below Table D2, in an equivalent amount to 50 weight % ofthe final polymer and Ethanox® 330 (CAS: 1709-70-2, 200 ppm based on thewt.-% Terathane Polyetherglycol) were then added together withtetrabutyl titanate (20 ppm Ti, Tyzor, DuPont, USA) as apolycondensation catalyst. The mixture was transferred to an autoclave.Over a time period of 90 minutes the pressure was reduced to <0.3 mm Hgwhile the temperature was ramped to 250° C. The reaction mixture washeld at this temperature until the required melt viscosity, as measuredby the stirrer amperage, was met. The reactor was pressurized slightlywith nitrogen and the product extruded into chilled water. After thepolymer strand cooled, it was pelletized with a Scheer-bay pelletizer.

The compositions of the final copolyester-ethers as well as the thermalbehavior are shown in Table D2 below.

TABLE D2 Sample 7 8 9 10 11 12 Terathane ® Polyetherglycol 250 650 10001400 2000 2900 [g/mol] Tm [° C.] — 181 206 224 241 245

As is evident from the above Tables D1 and D2, the melting point (T_(m))of the copolyester-ether depends in linear fashion on the molecularweight of the employed polyether.

Example D3—Synthesis of Starting Materials, Continuous PolymerizationProcess

Copolyester-ether was prepared using continuous polymerization process:A slurry of terephthalic acid and glycol in a small molar excess ofglycol (PTA/EG molar ratio <1:1.15) was continuously charged to theprimary esterification reactor. The amount of slurry added to theprimary esterification reactor was controlled by a flow measuringdevice. In the primary esterification reactor, terephthalic acid andglycol reacted at 250-260° C. and 2-4 bar excess pressure under waterelimination. The resulting low molecular weight esterification productwas then transferred (via pump) to another reactor (secondaryesterifier). A titanium catalyst and different amounts ofpoly(tetramethylene oxide) glycol (Terathane® Polyetherglycol, having anumber average molecular weight of 1400 g/mole, stabilized with 200 ppmEthanox® 330) based on the final polymer weight were then added to thereaction mixture. The amounts of Terathane® Polyetherglycol added andthe type of titanium catalyst used are indicated in below Table D3. Thepolycondensation, the elimination of glycol under reduced pressurestarted at 250-260° C. The dwell time of the reaction mixture(pre-condensate) was again controlled by a flow measuring device. Thepre-condensate was then discharged consecutively in two downstreamreactors where the dwell time was controlled via the level of thereaction mixture in each reactor. In both reaction vessels glycol wasdistilled out of the reaction mixture under increased temperature andreduced pressure until the desired polymerization degree was achieved.The desired polymer melt flowed through the reactor discharge pump intoa cooling bath filled with deionized water. After the polymer strandcooled, it was pelletized with a Pell-tec pelletizer.

The compositions of the final copolyester-ethers as well as the thermalbehavior are shown in Table D3 below

TABLE D3 Sample 13 14 15 16 17 19 20 21 22 23 18 Catalyst HS06² HS06HS06 HS06 HS06 TBT³ TBT TBT TBT TBT TBT Catalyst [ppm Ti]  14  13  13 13  17  32  30  28  29  15  22 Terathane ® 10/90 20/80 25/75 30/7043/57 20/80 27/73 43/57 50/50 50/50 0/100 Polyetherglycol/ PTA-EG¹ [wt.by wt.] T_(m) [° C.] 248 246 245 242 237 250 243 237 228 229 253 ¹PTA/EGratio: <1:1.15 ²Sacthleben ® Hombifast HS06 - Ti-based catalyst³TBT—Tetrabutyltitanat Tyzor ®, DuPont, USA

As is demonstrated in the above Table D3, the melting point (T_(m)) inboth types of polyester-ether copolymers (Samples 13-17 and 19-22)depends on the weight ratio of the polyether segment to the polyestersegment in linear fashion.

Example D4. Additional Copolyester-Esters

Further samples 24-34 were prepared following the process describedabove in Example D1 except that 25 ppm Ti (Sachtleben Hombifast HS06®)were used. The compositions of the final copolyester-ethers as well asthe thermal behavior are shown in Table D4 below.

TABLE D4 Mw Terathane ® wt.-%-ratio Terathane ® Sample Polyetherglycol[g/mol] Polyetherglycol/PTA-EG T_(m) [° C.] 24 650 15/85 244 25 1400 5/95 254 26 15/85 251 27 25/75 248 28 35/65 241 29 45/55 234 30 200015/85 253 31 35/65 248 32 2900 15/85 253 33 35/65 250

It is evident from samples 24-33, in particular from samples 25-29, thatthe melting point (T_(m)) of the copolyester-ether depends in linearfashion on the amount of the employed polyether in thecopolyester-ether.

Example D5—Preparation of Preforms/Bottles from Barrier/Base ResinBlend: Physical Properties and Delamination as Well as Barrier BehaviorSynthesis of the Base Polyester (BP)

The base resin was prepared using continuous process: A slurry ofterephthalic acid, isophthalic acid (3.05 wt.-% based on the finalpolymer) and glycol in a small molar excess of glycol (PTA/EG molarratio <1:1.08) was continuously charged to the primary esterificationreactor. The amount of slurry added to the primary esterificationreactor was controlled by a flow measuring device. In the primaryesterification reactor, terephthalic acid and glycol react at 250-260°C. and 2-4 bar excess pressure under water release. The resulting lowmolecular weight esterification product was then transferred (via pump)to another reactor (secondary esterifier). A titanium catalyst(Sachtleben Hombifast HS06, 7 ppm Ti based on the final polymer) wasthen added to the reaction mixture and the polycondensation, theelimination of glycol under reduced pressure started at 260-280° C. Thedwell time of the reaction mixture (pre-condensate) was again controlledby a flow measuring device. The pre-condensate was then dischargedconsecutively in two downstream reactors whereas the dwell time wascontrolled via level of the reaction mixture in each reactor. In bothreaction vessels further glycol was distilled out of the reactionmixture under increased temperature and reduced pressure until thedesired polymerization degree is achieved. The oxidation catalyst (75ppm cobalt as Cobalt-stearate, CAS: 1002-88-6) was added late as a meltto the reaction mixture shortly before the polymer melt flowed throughthe reactor discharge pump in a cooling bath with deionized water. Afterthe polymer strand cooled, it was pelletized with a Pell-tec pelletizer.

The resulting polymer chips were crystallized for approx. 4 hours at160° C., solid stated under vacuum at a temperature of 230° C. forapprox. 7 hours to the desired intrinsic viscosity value (˜IV-value:0.860 dl/g) and then cooled to ambient temperature.

Preforms/Bottles

Barrier resins as indicated in the below Table D5 were dried and blendedin varying amounts (from 2 to 10 wt.-%) with the dried base polyesterresin (BP1), and injection molded into preforms. The preforms werestretch blow molded into 500 mL, 28 g bottles. The oxygen permeation,the color values as well as the haze of these bottles were measured.

The compositions of the preforms and bottles as well as physicalproperties are depicted in Table D5. Table D5 further shows theobtainable delamination behavior.

TABLE D5 Bottle/Preform no. I II III IV³ Preform/Bottle Barrier resinsample 13 14 16 24 composition Terathane ® 10/90 20/80 30/70 50/50Polyetherglycol/ PTA-EG¹ [wt. by wt.] [wt.-%] 10 5 3.3 2 Base resin[wt.-%] 90.0 95.0 96.7 98.0 (BP1) Bottles Bottle IV (dl/g) 0.824 0.8190.808 0.829 properties L 89 88.7 88.5 87.3 a* 0.02 0.04 −0.02 0.19 b*3.12 3.6 4.42 5.26 Haze [%] 2.4 2.1 2.1 3 Delamination (Delamination +++++ + 0 test (bottles) Tendency²) Barrier [ppb] 22 24 43 44 performanceafter 28 days ¹PTA/EG ratio <1:1.15 ²first delamination test, +++:excellent, no delamination detected ++: very good, almost nodelamination detected; +: good: some delamination detected in somebottles 0: poor, delamination detected in most bottles ³commercial resinOxyclear ® 3500 barrier resin

Those bottles falling within the scope of the present invention(bottle/preforms I, II, and III obtained from samples 13, 14 and 16) aresubstantially superior in their delamination behavior to comparablesamples outside of the scope (sample IV obtained from sample 24). Thebottles falling within the scope of the present invention have excellentbarrier properties.

Example D6—Preparation of Preforms/Bottles from Barrier/Base ResinBlends: Delamination Properties

The samples 24-33 prepared in Example D4 were dried and blended invarying amounts with the dried base polyester resin (resin 2300K,obtainable from INVISTA, m.p. 244.5° C.) to obtain a final polyetherconcentration of 1 or 7 wt.-%, and injection molded into preforms. Thepreforms were stretch blow molded into 500 mL, 28 g bottles, accordingto the previously described procedure. The bottle compositions areindicated in the below Table D6:

TABLE D6 COPE wt.-%-ratio Terathane ® Terathane ® PolyetherglycolPolyetherglycol/ Polyether in bottle Sample [g/mol] PTA-EG (wt.-%) 341400  5/95 1 35 1400 15/85 1 36 1400 25/75 1 37 1400 35/65 1 38 140045/55 1 39 1400 35/65 7 10 250 35/65 1 41 650 15/85 1 42 2000 15/85 1 432000 35/65 1 44 2900 15/85 1 45 2900 35/65 1

The bottles prepared from samples 34 to 45 were tested for delaminationaccording to the second delamination test. All bottles showed improveddelamination (i.e. lower total numbers of delaminated bottles) thanbottles prepared from comparative reference sample 23.

Example D7. Preparation of Preforms/Bottles from Barrier/Base ResinBlends: Delamination Properties

Samples of copolyester-ethers prepared in Example D4 were dried andblended in varying amounts with the dried base polyester resin (resin2300K, obtainable from INVISTA, m.p. 244.5° C.) to obtain a finalpolyether concentration of 1 wt.-%, and injection molded into preforms.The preforms were stretch blow molded into 500 mL, 28 g bottles,according to the previously described procedure. The bottle compositionsare indicated in the below Table D7. The prepared bottles were testedfor delamination according to the third delamination test.

TABLE D7 Copolyester-ether (COPE) wt.-%-ratio ΔT Amount of Terathane ®Terathane ® (m.p. base resin − delami- Sam- PolyetherglycolPolyetherglycol/ m.p. COPE) nation ple [g/mol] PTA-EG (° C.) (cm) 461400 15/85 6.5 0.75 47 1400 45/55 10.5 2.54 48 2900 15/85 8.5 1.37 492900 35/65 5.5 0.9

The above table demonstrates that bottles prepared according to theinvention show a low amount of delamination. In addition, delaminationdecreased in the above examples with decreasing temperature differencebetween the melting points of the base resin and the copolyester-ether.

Example D8. Preparation of Preforms/Bottles from Barrier/Base ResinBlends: Delamination Properties

In order to compare the influence of the base resin on delaminationperformance, the following base resins compositions were prepared which,like resin 2300K base resin, comprise 83 ppm cobalt as oxidationcatalyst.

TABLE D8 T_(m) of base Polyester Catalyst Co [ppm] resin (° C.) 7090 Ti83   225° C. T94N Sb 83 240.9° C. 1101 Sb 83 245.7° C. BRC Ti 83   242°C. 2300K Sb 83 244.5° C.

Resins 7090, T94N and 1101 are commercially available from INVISTA.Resin BRC was prepared as follows in Example D9-D10.

Example D9. Synthesis of the Base Polyester (BRC)

The base resin BRC was prepared using continuous process: A slurry ofterephthalic acid, isophthalic acid (3.05 wt.-% based on the finalpolymer) and glycol in a small molar excess of glycol (PTA/EG molarratio <1:1.08) was continuously charged to the primary esterificationreactor. The amount of slurry added to the primary esterificationreactor was controlled by a flow measuring device. In the primaryesterification reactor terephthalic acid and glycol react at 250-260° C.and 2-4 bar excess pressure under water release. The resulting lowmolecular weight esterification product was then transferred (via pump)to another reactor (secondary esterifier). A titanium catalyst(Sachtleben Hombifast HS06®, 7 ppm Ti based on the final polymer) wasthen added to the reaction mixture and the polycondensation, theelimination of glycol under reduced pressure, started at 260-280° C. Thedwell time of the reaction mixture (pre-condensate) is again controlledby a flow measuring device. The pre-condensate was then dischargedconsecutively in two downstream reactors whereas the dwell time wascontrolled via level of the reaction mixture in each reactor. In bothreaction vessels further glycol was distilled out of the reactionmixture under increased temperature and reduced pressure until thedesired polymerization degree is achieved. The polymer melt flowedthrough the reactor discharge pump in a cooling bath with deionizedwater. After the polymer strand cooled, it was pelletized with Pell-tecpelletizer.

The resulting polymer chips were crystallized for approx. 4 hours at160° C., solid stated under vacuum at a temperature of 230° C. forapprox. 7 hours to the desired intrinsic viscosity value (˜IV-value:0.860 dl/g) and then cooled to ambient temperature.

Example D10—Compounding of Base Resins with the Catalyst

The different Base Resins described above (except 2300K) were used forcompounding. Prior to the extrusion the Base Resins were dried at 160°C. under vacuum for 5 hours to remove residual moisture. The Base Resinswere then added to an intermeshing, co-rotating, twin screw extrudermanufactured by Leistritz AG. The oxidation catalyst (83 ppm Cobalt asCobalt-stearate, CAS: 1002-88-6) was added as a melt to the meltedpolymer via side addition pump and the reaction mixture weresubsequently further extruded, before the polymer melt flowed throughthe reactor discharge pump in a cooling bath with deionized water. Theprocess conditions used during the experiment are described below:

-   -   Extruder type: (Leistritz Micro 27 36D), co-rotating, extruder        screw diameter 27 mm, screw length to diameter ratio (L:D) ratio        is 36:1    -   Operation conditions: T0 cooling water temperature/T1 240° C./T2        258° C./T3 262/T4-T5 268° C./T6-T8 273° C./T9 269° C.    -   No vacuum level in degassing area    -   Polymer flow rate 8 kg/h    -   Type of granules: cylindrical, length 3 mm and diameter 2 mm

Example D11—Preforms and Bottles

Samples of copolyester-ethers prepared in Example D4 were dried andblended with the polyester base resin compositions prepared ion aboveExample D10 or resin 2300K so that a final polyether concentration of 1wt.-% was obtained. The blend was injection molded into preforms. Thepreforms were stretch blow molded into 500 mL, 28 g bottles, accordingto the previously described procedure. The bottle compositions areindicated in the below Table D9. The prepared bottles were tested fordelamination according to the third delamination test:

TABLE D9 Copolyester-ether (COPE) wt.-%-ratio Terathane ® Terathane ®Polyetherglycol Polyetherglycol/ Delamination Sample Polyester [g/mol]PTA-EG (cm) 50 7090 1400 45/55 4.21 51 T94N 1400 45/55 4.79 52 BRC 140045/55 4.04 53 1101 1400 45/55 4.63 54 2300K 1400 45/55 2.54

The above table demonstrates that bottles prepared according to theinvention but using different polyester base resins do provide similarperformance.

This application claims the benefit of priority of EP 13199102.8, filed20 Dec. 2013, EP 13199112.7, filed 20 Dec. 2013, EP 13199125.9, filed 20Dec. 2013, EP 13199131.7, filed 20 Dec. 2013, U.S. Ser. No. 62/069,236,filed 27 Oct. 2014, U.S. Ser. No. 62/069,239, filed 27 Oct. 2014, U.S.Ser. No. 62/069,252, filed 27 Oct. 2014, and U.S. Ser. No. 62/069,258,filed 27 Oct. 2014, each of which is incorporated herein by reference inits entirety.

While the invention has been described in conjunction with specificembodiments thereof, it is understood that many alternatives,modifications, and variations will be apparent to those skilled in theart in light of the foregoing description. Accordingly, it is intendedto embrace all such alternatives, modifications, and variations as fallwithin the spirit and scope of the appended embodiments.

EMBODIMENTS First Aspect

-   1. A composition for preparing an article, preform or container    comprising:    -   a) 80-98.5 parts by weight of a base polyester;    -   b) 0.5-20 parts by weight of a copolyester-ether,        -   wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments,            wherein the one or more polyether segments are present in an            amount of about 5 to about 95 wt.-% of the            copolyester-ether;    -   c) a transition metal-based oxidation catalyst; and    -   d) a monomeric, oligomeric or polymeric hindered amine light        stabilizer (HALS) in an amount of 15-10,000 ppm, on basis of the        weight of the stabilizer in the total composition, wherein the        HALS is represented by the formula (I) or a mixture of compounds        of formula (I),

-   -   wherein each R₁ independently represents C₁-C₄ alkyl, R₂        represents H, C₁-C₄ alkyl, OH, O—C₁-C₄ alkyl, or a further part        of an oligomeric or polymeric HALS, and R₃ represents a further        part of a monomeric, oligomeric or polymeric HALS.

-   2. The composition of embodiment 1, wherein the polyether segment is    a linear or branched poly (C₂-C₆-alkylene glycol) segment.

-   3. The composition of embodiment 1 or 2, wherein the polyether    segment has a number-average molecular weight of about 200 to about    5000 g/mol, preferably about 600 to about 2500 g/mol.

-   4. The composition of any one of embodiments 1 to 3, wherein the    polyether segments are present in the copolyester-ether in an amount    of about 20 to about 40 wt.-%.

-   5. The composition of any one of embodiments 1 to 4, wherein the    copolyester-ether comprises a polyethylene terephthalate    (co)polyester segment.

-   6. The composition of any one of embodiments 1 to 5, wherein the    HALS is a monomeric HALS, preferably having a molecular weight of    400 g/mol or above.

-   7. The composition of any one of embodiments 1 to 5, wherein the    HALS is an oligomeric or polymeric HALS.

-   8. The composition of embodiment 7, wherein the HALS is an    oligomeric or polymeric HALS comprising one or more moieties of the    formula (I),

-   -   wherein each R₁ independently represents C₁-C₄ alkyl, R₂        represents H or C₁-C₄ alkyl, and R₃ represents a further part of        the oligomeric or polymeric HALS.

-   9. The composition of any one of embodiments 1 to 8, wherein the    HALS is present in an amount of about 20 to about 2500 ppm.

-   10. The composition of any one of embodiments 1 to 9, wherein    transition metal-based oxidation catalyst is a cobalt compound.

-   11. The composition of any one of embodiments 1 to 10, wherein the    copolyester-ether and/or the polyester is produced using a    titanium-based polycondensation catalyst.

-   12. The composition of embodiment 11, wherein the weight ratio of    titanium metal to HALS is 1:2 to 1:500.

-   13. The composition of any one of embodiments 1 to 12, wherein the    transition metal-based oxidation catalyst is present in an amount of    from about 15 to about 400 ppm based on the weight of the transition    metal in the total composition

-   14. The composition of any one of embodiments 1 to 13, wherein the    weight ratio of the one or more polyether segments to the total    amount of base polyester and polyester segments in the composition    is from about 0.2 to about 10 wt. %.

-   15. A masterbatch for use in preparing an article, preform or    container comprising:    -   a) copolyester-ether,        -   wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments,            wherein the one or more polyether segments are present in an            amount of about 5 to about 95 wt.-% of the            copolyester-ether; and    -   b) a monomeric, oligomeric or polymeric hindered amine light        stabilizer (HALS) in an amount of 100-30,000 ppm, on basis of        the weight of the stabilizer in the total composition, wherein        the HALS is represented by the formula (I) or a mixture of        compounds of formula (I),

-   -   wherein each R₁ independently represents C₁-C₄ alkyl, R₂        represents H, C₁-C₄ alkyl, OH, O—C₁-C₄ alkyl, or a further part        of an oligomeric or polymeric HALS, and R₃ represents a further        part of a monomeric, oligomeric or polymeric HALS.

-   16. The masterbatch of embodiment 15, wherein the polyether segment    is a linear or branched poly (C₂-C₆-alkylene glycol) segment.

-   17. The masterbatch of embodiment 15 or 16, wherein the polyether    segment has a number-average molecular weight from 200 to about 5000    g/mol, preferably about 600 to about 2500 g/mol.

-   18. The masterbatch of any one of embodiments 15 to 16, wherein the    polyether segments are present in the copolyester-ether in an amount    of about 20 to about 40 wt.-%.

-   19. The masterbatch of any one of embodiments 15 to 18, wherein the    copolyester-ether comprises a polyethylene terephthalate    (co)polyester segment.

-   20. The masterbatch of any one of embodiments 15 to 19, wherein the    HALS is a monomeric HALS, preferably having a molecular weight of    400 g/mol or above.

-   21. The masterbatch of any one of embodiments 15 to 19, wherein the    HALS is an oligomeric or polymeric HALS.

-   22. The masterbatch of embodiment 21, wherein the HALS is an    oligomeric or polymeric HALS comprising one or more moieties of the    formula (I),

-   -   wherein each R₁ independently represents C₁-C₄ alkyl, R₂        represents H or C₁-C₄ alkyl, and R₃ represents a further part of        the oligomeric or polymeric HALS.

-   23. The masterbatch of any one of embodiments 15 to 22, wherein the    HALS is present in an amount of about 250 to about 10,000 ppm.

-   24. The masterbatch of any one of embodiments 15 to 23, wherein the    copolyester is prepared using a titanium-based polycondensation    catalyst.

-   25. The masterbatch of any one of embodiments 15 to 23, further    comprising a titanium compound.

-   26. The masterbatch of embodiment 24 or 25, wherein weight ratio of    titanium metal to HALS is 1:2 to 1:500

-   27. The masterbatch or composition of any one of embodiments 1 to    26, wherein the weight ratio of the transition metal-based oxidation    catalyst to the HALS is 100:1 to 1:50.

-   28. An article, preform or container prepared from a composition of    any one of embodiments 1 to 27.

-   29. A method of preparing a masterbatch for use in preparing an    article, preform or container comprising mixing a copolyester-ether,    wherein the copolyester-ether comprises one or more polyester    segments and one or more polyether segments, wherein the one or more    polyether segments are present in an amount of about 5 to about 95    wt.-% in the copolyester-ether; with a monomeric, oligomeric or    polymeric hindered amine light stabilizer (HALS) in an amount of    100-30,000 ppm, on basis of the weight of the stabilizer in the    total composition, wherein the HALS is represented by the    formula (I) or a mixture of compounds of formula (I),

-   -   wherein each R₁ independently represents C₁-C₄ alkyl, R₂        represents H, C₁-C₄ alkyl, OH, O—C₁-C₄ alkyl, or a further part        of an oligomeric or polymeric HALS, and R₃ represents a further        part of a monomeric, oligomeric or polymeric HALS.

-   30. A method of preparing a composition for use in preparing an    article, preform or container comprising mixing 80-98.5 parts by    weight of a base polyester with:    -   a) 0.5-20 parts by weight of a copolyester-ether,        -   wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments,            wherein the one or more polyether segments are present in an            amount of about 5 to about 95 wt.-% of the            copolyester-ether;    -   b) a transition metal-based oxidation catalyst; and    -   c) a monomeric, oligomeric or polymeric hindered amine light        stabilizer (HALS) in an amount of 15-10,000 ppm, on basis of the        weight of the stabilizer in the total composition, wherein the        HALS is represented by the formula (I) or a mixture of compounds        of formula (I),

-   -   wherein each R₁ independently represents C₁-C₄ alkyl, R₂        represents H, C₁-C₄ alkyl, OH, O—C₁-C₄ alkyl, or a further part        of an oligomeric or polymeric HALS, and R₃ represents a further        part of a monomeric, oligomeric or polymeric HALS.

-   31. Use of a monomeric, oligomeric or polymeric hindered amine light    stabilizer (HALS), wherein the HALS is represented by the    formula (I) or a mixture of compounds of formula (I),

-   -   wherein each R₁ independently represents C₁-C₄ alkyl, R₂        represents H, C₁-C₄ alkyl, OH, O—C₁-C₄ alkyl, or a further part        of an oligomeric or polymeric HALS, and R₃ represents a further        part of a monomeric, oligomeric or polymeric HALS; for reducing        the amount of decomposition products in an article, preform or        container comprising: 80-98.5 parts by weight of a base        polyester; 0.5-20 parts by weight of a copolyester-ether,        wherein the copolyester-ether comprises one or more polyester        segments and one or more polyether segments, wherein the one or        more polyether segments are present in an amount of about 5 to        about 95 wt.-% of the copolyester-ether; and a transition        metal-based oxidation catalyst.

Second Aspect

-   1. A composition for preparing articles, preforms or containers    comprising:    -   a) 80-99.5 parts by weight of a base polyester;    -   b) 0.5-20 parts by weight of a copolyester-ether, wherein the        copolyester-ether comprises one or more polyester segments and        one or more polyether segments;    -   c) a transition metal-based oxidation catalyst,        -   c1) wherein the transition metal is selected from cobalt,            manganese, copper, chromium, zinc, iron, and nickel, and        -   c2) wherein the transition metal based oxidation catalyst is            present in an amount of 10-500 ppm, on basis of the weight            of the transition metal in the total composition; and    -   d) a titanium compound,    -   wherein the weight ratio of the transition metal-based oxidation        catalyst to the titanium compound, on basis of the weight of the        transition metal and the titanium, is from 50:1 to 1:1.-   2. The composition of embodiment 1, wherein the polyether segment is    a linear or branched poly (C₂-C₆-alkylene glycol) segment.-   3. The composition of embodiment 1 or 2, wherein the polyether    segment has a number-average molecular weight of from about 200 to    about 5000 g/mol, preferably from about 600 to about 2500 g/mol.-   4. The composition of any one of embodiments 1 to 3, wherein the    amount of titanium in the total composition is less than the amount    of the transition metal of the transition metal based oxidation    catalyst in the total composition.-   5. The composition of any one of embodiments 1 to 4, wherein the    titanium compound is present in an amount of 5 to 20 ppm, on basis    of the weight of titanium in the total composition, and wherein the    transition metal based oxidation catalyst is present in an amount of    30 to 200 ppm, on basis of the weight of the transition metal in the    total composition.-   6. The composition of any one of embodiments 1 to 5, wherein the    amount of titanium in the total composition is between 3 and 15 ppm.-   7. The composition of any one of embodiments 1 to 6, wherein the    titanium compound is a polycondensation and/or transesterfication    catalyst.-   8. The composition of any one of embodiments 1 to 7, wherein    transition metal-based oxidation catalyst is a cobalt compound.-   9. The composition of any one of embodiments 1 to 8, wherein the    copolyester-ether comprises a polyethylene terephthalate    (co)polyester segment.-   10. The composition of any one of embodiments 1 to 9, wherein the    polyester is a polyethylene terephthalate (co)polyester.-   11. A kit-of-parts for use in preparing articles, preforms or    containers comprising two masterbatches which may optionally be in    admixture:    -   a first masterbatch comprising:    -   a) a base polyester,    -   b) a transition metal-based oxidation catalyst, wherein the        transition metal is selected from cobalt, manganese, copper,        chromium, zinc, iron, and nickel, and    -   c) a titanium compound, wherein the titanium compound is present        in an amount of about 5 to about 500 ppm, on basis of the weight        of the titanium in the first masterbatch; and    -   a second masterbatch comprising:    -   d) a copolyester-ether; and optionally    -   e) one or more antioxidants.-   12. The kit-of-parts of embodiment 11, wherein the kit-of-parts is    packaged for storage.-   13. The kit-of-parts of embodiment 11 or 12, wherein the transition    metal based oxidation catalyst is present in an amount of 500-15000    ppm, on basis of the weight of the transition metal in first    masterbatch.-   14. The kit-of-parts of any one of embodiments 11 to 13, wherein the    second masterbatch comprises an antioxidant selected from group    consisting of hindered phenols, benzophenones, sulfur-based    antioxidants, phosphites and hindered amine light stabilizer.-   15. The kit-of-parts of any one of embodiments 11 to 14, wherein the    weight ratio of the transition metal-based oxidation catalyst to the    titanium compound, on basis of the weight of the transition metal    and the titanium, is from 5:1 to 500:1 in the first masterbatch.-   16. The kit-of-parts of any one of embodiments 11 to 15, wherein    transition metal-based oxidation catalyst is a cobalt compound in    the first masterbatch.-   17. The kit-of-parts of any one of embodiments 11 to 16, wherein the    second masterbatch comprises a titanium compound.-   18. An article, preform or container prepared from a composition or    kit-of-parts of any one of embodiments 1 to 17.-   19. A method of preparing a composition for use in preparing    articles, preforms or containers comprising mixing:    -   a) 80-99.5 parts by weight of a base polyester;    -   b) 0.5-20 parts by weight of a copolyester-ether, wherein the        copolyester-ether comprises one or more polyester segments and        one or more polyether segments;    -   c) a transition metal-based oxidation catalyst,        -   c1) wherein the transition metal is selected from cobalt,            manganese, copper, chromium, zinc, iron, and nickel, and        -   c2) wherein the transition metal based oxidation catalyst is            present in an amount of 10-500 ppm, on basis of the weight            of the transition metal in the total composition; and    -   d) a titanium compound;    -   wherein the weight ratio of the transition metal-based oxidation        catalyst to the titanium compound, on basis of the weight of the        transition metal and the titanium, is from 50:1 to 1:1.-   20. A method of preparing a kit-of-parts for use in preparing    articles, preforms or containers comprising combining two    masterbatches, the first masterbatch comprising:    -   a) a base polyester,    -   b) a transition metal-based oxidation catalyst, wherein the        transition metal is selected from cobalt, manganese, copper,        chromium, zinc, iron, and nickel, and    -   c) a titanium compound, wherein the titanium compound is present        in an amount of about 5 to about 500 ppm, on basis of the weight        of the titanium in the first masterbatch; and    -   the second masterbatch comprising:    -   d) a copolyester-ether; and optionally    -   e) one or more antioxidants.

Third Aspect

-   1. A composition for preparing articles, preforms or containers    comprising:    -   a) 80-99.5 parts by weight of a base polyester;    -   b) 0.5-20 parts by weight of a copolyester-ether,        -   b1) wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments, and        -   b2) wherein the one or more polyether segments are present            in the copolyester-ether in an amount of 5 to 45 wt.-%;    -   c) a transition metal-based oxidation catalyst,        -   c1) wherein the transition metal is selected from cobalt,            manganese, copper, chromium, zinc, iron, and nickel, and        -   c2) wherein the transition metal based oxidation catalyst is            present in an amount of 10-500 ppm, on basis of the weight            of the transition metal in the total composition; and    -   d) a titanium compound.-   2. The composition of embodiment 1, wherein the polyether segment is    a linear or branched poly (C₂-C₆-alkylene glycol) segment.-   3. The composition of embodiment 1 or 2, wherein the polyether    segment has a number-average molecular weight of about 200 to about    5000 g/mol, preferably about 600 to 2500 g/mol.-   4. The composition of any one of embodiments 1 to 3, wherein the    polyether segments are present in the copolyester-ether in an amount    of 10 to 40 wt.-%.-   5. The composition of embodiment 4, wherein polyether segments are    present in the copolyester-ether in an amount of 20 to 35 wt.-%.-   6. The composition of any one of embodiments 1 to 5, wherein the    copolyester-ether comprises a polyethylene terephthalate    (co)polyester segment.-   7. The composition of any one of embodiments 1 to 6, wherein the    amount of titanium in the total composition is less than the amount    of the transition metal of the transition metal based oxidation    catalyst in the total composition.-   8. The composition of any one of embodiments 1 to 7, wherein the    titanium compound is present in an amount of 5 to 20 ppm, on basis    of the weight of titanium in the total composition, and wherein the    transition metal based oxidation catalyst is present in an amount of    30 to 200 ppm, on basis of the weight of the transition metal in the    total composition.-   9. The composition of any one of embodiments 1 to 8, wherein the    titanium compound is a polycondensation and/or transesterfication    catalyst.-   10. The composition of any one of embodiments 1 to 9, wherein    transition metal-based oxidation catalyst is a cobalt compound.-   11. The composition of any one of embodiments 1 to 10, wherein the    polyester is a polyethylene terephthalate (co)polyester.-   12. A kit-of-parts for use in preparing articles, preforms or    containers comprising two masterbatches which may optionally be in    admixture:    -   the first masterbatch comprising:    -   a) a base polyester,    -   b) a transition metal-based oxidation catalyst, wherein the        transition metal is selected from cobalt, manganese, copper,        chromium, zinc, iron, and nickel, and wherein the transition        metal based oxidation catalyst is present in an amount of        500-15000 ppm, on basis of the weight of the transition metal in        first masterbatch,    -   c) a titanium compound; and    -   the second masterbatch comprising:    -   d) a copolyester-ether,        -   d1) wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments,            wherein the one or more polyether segments are present in an            amount of 5 and 45 wt.-% in the copolyester-ether; and            optionally    -   e) one or more antioxidants.-   13. The kit-of-parts of embodiment 12, wherein the kit-of-parts is    packaged for storage.-   14. The kit-of-parts of embodiment 12 or 13, wherein the titanium    compound is present in an amount of about 5 to about 500 ppm, on    basis of the weight of the titanium in the first masterbatch.-   15. The kit-of-parts of any one of embodiments 12 to 14, wherein the    transition metal based oxidation catalyst is present in an amount of    1000-10000 ppm, on basis of the weight of the transition metal in    first masterbatch.-   16. The kit-of-parts of any one of embodiments 12 to 15, wherein the    second masterbatch comprises an antioxidant selected from group    consisting of hindered phenols, benzophenones, sulfur-based    antioxidants, phosphites and hindered amine light stabilizer.-   17. The kit-of-parts of any one of embodiments 12 to 16, wherein the    weight ratio of the transition metal-based oxidation catalyst to the    titanium compound, on basis of the weight of the transition metal    and the titanium, is from 5:1 to 500:1 in the first masterbatch.-   18. The kit-of-parts of any one of embodiments 12 to 17, wherein    transition metal-based oxidation catalyst is a cobalt compound in    the first masterbatch.-   19. The kit-of-parts of any one of embodiments 12 to 18, wherein the    second masterbatch comprises a titanium compound.-   20. An article, preform or container prepared from a composition or    kit-of-parts of any one of embodiments 1 to 19.-   21. A method of preparing a composition for use in preparing    articles, preforms or containers comprising mixing:    -   a) 80-99.5 parts by weight of a base polyester;    -   b) 0.5-20 parts by weight of a copolyester-ether,        -   b1) wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments, and        -   b2) wherein the one or more polyether segments are present            in the copolyester-ether in an amount of 5 to 45 wt.-%;    -   c) a transition metal-based oxidation catalyst,        -   c1) wherein the transition metal is selected from cobalt,            manganese, copper, chromium, zinc, iron, and nickel, and        -   c2) wherein the transition metal based oxidation catalyst is            present in an amount of 10-500 ppm, on basis of the weight            of the transition metal in the total composition; and    -   d) a titanium compound.-   22. A method of preparing a kit-of-parts for use in preparing    articles, preforms or containers comprising combining two    masterbatches,    -   the first masterbatch comprising:    -   a) a base polyester,    -   b) a transition metal-based oxidation catalyst, wherein the        transition metal is selected from cobalt, manganese, copper,        chromium, zinc, iron, and nickel, and wherein the transition        metal based oxidation catalyst is present in an amount of        500-15000 ppm, on basis of the weight of the transition metal in        first masterbatch,    -   c) a titanium compound; and    -   the second masterbatch comprising:    -   d) a copolyester-ether,        -   d1) wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments, and        -   d2) wherein the one or more polyether segments are present            in an amount of 5 and 45 wt.-% in the copolyester-ether; and            optionally    -   e) one or more antioxidants.

Fourth Aspect

-   1. A composition for preparing articles, preforms or containers    comprising:    -   a) 80-99.5 parts by weight of a base polyester;    -   b) 0.5-20 parts by weight of a copolyester-ether,        -   wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments,            wherein the one or more polyether segments are present in an            amount of about 5 to about 45 wt.-% of the            copolyester-ether; and    -   c) a transition metal-based oxidation catalyst;    -   wherein the melting point difference, determined according to        ASTM D 3418-97, between the base polyester and the        copolyester-ether is less than 15° C.-   2. The composition of embodiment 1, wherein the polyether segment is    a linear or branched poly (C₂-C₆-alkylene glycol) segment.-   3. The composition of embodiment 1 or 2, wherein the polyether    segment has a number-average molecular weight from about 200 to    about 5000 g/mol, preferably from about 600 to about 2500 g/mol.-   4. The composition of any one of embodiments 1 to 3, wherein the    polyether segments are present in the copolyester-ether in an amount    of about 20 to about 35 wt.-%.-   5. The composition of any one of embodiments 1 to 4, wherein the    copolyester-ether comprises a polyethylene terephthalate    (co)polyester segment.-   6. The composition of any one of embodiments 1 to 5, wherein the    base polyester is polyethylene terephthalate or a copolymer thereof    and has a melting point, determined according to ASTM D 3418-97, of    about 240 to about 250° C.-   7. The composition of any one of embodiments 1 to 6, wherein the    melting point difference, determined according to ASTM D 3418-97,    between the base polyester and the copolyester-ether is less than    about 8° C.-   8. The composition of any one of embodiments 1 to 7, wherein    transition metal-based oxidation catalyst is a cobalt compound.-   9. The composition of any one of embodiments 1 to 8, wherein the    transition metal-based oxidation catalyst is present in an amount of    from about 10 to about 500 ppm based on the weight of the transition    metal in the total composition.-   10. The composition of any one of embodiments 1 to 9, wherein the    weight ratio of the one or more polyether segments to the total    amount of base polyester and polyester segments in the composition    is from about 0.2 to about 10 wt. %.-   11. An article, preform or container comprising or prepared from a    composition according to any one of embodiments 1 to 10.-   12. A masterbatch for use in preparing articles, preforms or    containers comprising:    -   a) a copolyester-ether,        -   a1) wherein the copolyester-ether comprises one or more            polyethylene terephthalate (co)polyester segments and one or            more linear or branched poly (C₂-C₆-alkylene glycol)            segments, and        -   a2) wherein the one or more polyether segments are present            in an amount of about 5 to about 45 wt.-% in the            copolyester-ether, and        -   a3) wherein the melting point, determined according to ASTM            D 3418-97, of the copolyester-ether is from about 225° C. to            about 250° C.; and    -   b) 20-5000 ppm, on basis of the weight of the one or more linear        or branched poly (C₂-C₆-alkylene glycol) segments, of one or        more antioxidants selected from group consisting of hindered        phenols, benzophenones, sulfur-based antioxidants, phosphites        and hindered amine light stabilizers.-   13. The masterbatch of embodiment 12, wherein the copolyester-ether    comprises one or more poly (butylene glycol) or poly (propylene    glycol) segments, wherein the one or more poly (butylene glycol) or    poly (propylene glycol) segments are present in an amount of about    20 to 35 wt.-% in the copolyester-ether, and wherein the melting    point, determined according to ASTM D 3418-97, of the    copolyester-ether is from about 225° C. to about 250° C.-   14. The masterbatch of embodiments 12 or 13, wherein the poly    (C₂-C₆-alkylene glycol) segments have a number-average molecular    weight from about 600 to about 2500 g/mol, preferably from about 600    to about 1800 g/mol.-   15. A copolyester-ether comprising one or more polyethylene    terephthalate (co)polymer segments and one or poly(butylene glycol)    or poly(propylene glycol) segments, wherein the one or more    poly(butylene glycol) or poly(propylene glycol) segments are present    in an amount of about 20 to about 35 wt.-% in the copolyester-ether,    and having a melting point, determined according to ASTM D 3418-97,    of from about 225° C. to about 250° C.-   16. The copolyester-ether of embodiment 15, wherein the poly    (butylene glycol) or poly (propylene glycol) segments have a number    average molecular weight of about 600 to about 1800 g/mol.-   17. A method of preparing an article, preform or container, wherein    80-99.5 parts by weight of a base polyester are blended with:    -   a) 0.5-20 parts by weight of a copolyester-ether,        -   wherein the copolyester-ether comprises one or more            polyester segments and one or more polyether segments,            wherein the one or more polyether segments are present in an            amount of about 5 to about 45 wt.-% of the            copolyester-ether, and    -   b) a transition metal-based oxidation catalyst;        -   wherein the melting point difference, determined according            to ASTM D 3418-97, between the base polyester and the            copolyester-ether is less than 15° C.-   18. Use of a copolyester-ether for preparing an article, preform or    container, wherein the copolyester-ether comprises one or more    polyester segments and one or more polyether segments, wherein the    one or more polyether segments are present in the copolyester-ether    in an amount from about 5 to about 45 wt.-%, and wherein the melting    point of the copolyester-ether, determined according to ASTM D    3418-97, is from about 225° C. to about 250° C.; for preparing an    article, preform or container.-   19. Use of a copolyester-ether, wherein the copolyester-ether    comprises one or more polyester segments and one or more polyether    segments, wherein the one or more polyether segments are present in    the copolyester-ether in an amount from about 5 to about 45 wt.-%,    and wherein the melting point of the copolyester-ether, determined    according to ASTM D 3418-97, is from about 225° C. to about 250° C.;    for preparing a kit-of-parts comprising said copolyester-ether and    physical or electronic instructions or advise to use said    copolyester-ether for preparing an article, preform or container.

1-13. (canceled)
 14. A masterbatch for use in preparing an article,preform or container comprising: a) copolyester-ether, wherein thecopolyester-ether comprises one or more polyester segments and one ormore polyether segments, wherein the one or more polyether segments arepresent in an amount of about 5 to about 95 wt.-% of thecopolyester-ether; and b) a monomeric, oligomeric or polymeric hinderedamine light stabilizer (HALS) in an amount of 100-30,000 ppm, on basisof the weight of the stabilizer in the total composition, wherein theHALS is represented by the formula (I) or a mixture of compounds offormula (I),

wherein each R₁ independently represents C₁-C₄ alkyl, R₂ represents H,C₁-C₄ alkyl, OH, O—C₁-C₄ alkyl, or a further part of an oligomeric orpolymeric HALS, and R₃ represents a further part of a monomeric,oligomeric or polymeric HALS; wherein the masterbatch does not containinorganic pigments in an amount of above 0.6 wt.-% of the totalmasterbatch and wherein the masterbatch does not contain carbon black inan amount of above 1.2 wt.-% of the total masterbatch.
 15. Themasterbatch of claim 14, wherein the polyether segment is a linear orbranched poly (C₂-C₆-alkylene glycol) segment.
 16. The masterbatch ofclaim 14, wherein the polyether segment a linear or branchedpoly(propylene glycol) or a linear or branched poly(butylene glycol)segment.
 17. The masterbatch of claim 14, wherein the polyether segmenthas a number-average molecular weight from 200 to about 5000 g/mol,preferably about 600 to about 2500 g/mol. 18-22. (canceled)
 23. Themasterbatch of claim 14, wherein the HALS is an oligomeric or polymericHALS comprising one or more moieties of the formula (I),

wherein each R₁ independently represents C₁-C₄ alkyl, R₂ represents H orC₁-C₄ alkyl, and R₃ represents a further part of the oligomeric orpolymeric HALS. 24-29. (canceled)
 30. A kit-of-parts for use inpreparing articles, preforms or containers comprising two masterbatcheswhich may optionally be in admixture, wherein the second of the twomasterbatches is the masterbatch of claim
 14. 31-35. (canceled)